SOLAR PHOTOCHEMICAL TECHNOLOGY
FOR POTABLE WATER TREATMENT:
DISINFECTION AND DETOXIFICATION
By
ADRIENNE TERESA COOPER
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNP7ERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1998
Copyright 1998
Adrienne Teresa Cooper
This dissertation is dedicated to my grandmothers, Gewenith
Manning and the late Ethel Cummings, who were women for their time
and to my nephew Fatin D. Cooper who is the future.
ACKNOWLEDGMENTS
The research conducted for this dissertation was supported by the
National Science Foundation through the University of Florida College of
Engineering Minority Engineering Doctoral Initiative.
Appreciation is expressed to my committee chairman Dr. Thomas
Crisman and cochairman Dr. D. Y. Goswami for their sage advice and
unwavering support over the last few years. Acknowledgment and
gratitude are extended to committee member Dr. Michael Annable for his
support and generous provision of access to analytical equipment and
laboratory facilities; to committee member Dr. Seymour S. Block whose
knowledge of disinfection has served as a valuable resource and who
graciously allowed me the use of his laboratory; committee member Dr.
Paul Chadik, who helped to steer me in the right direction from the very
beginning; to Sanjay Puranik for sharing his knowledge of analytical
chemistry; to Chuck Garretson for making available his wealth of
mechanical capabilities, keen insight and ever present smile; to Michael
McCaskill and Michael Oliver for their diligent assistance in the
laboratory; and to Barbara Walker and Berdenia Monroe for their
administrative support and friendship. My gratitude and thanks are due to
committee member Dr. Jonathan Earle for his guidance, encouragement,
confidence and that extra push when I needed it.
IV
The insight, support and friendship of my colleagues in the Solar
Energy Group, the Center for Wetlands and Environmental Engineering
Sciences have truly enriched my learning experience here at the University
of Florida, and they, in their own ways, have contributed to the achievement
of this goal.
A special thank you is extended to the entire Earle family, Celia,
Jeremy, Kevin and Mrs. Yvonne Earle, for being my "Gainesville Family."
My parents Dr. and Mrs. Trenton Cooper, my sister Mrs. Edris
Anifowoshe, and my nephew, Fatin Cooper, have provided invaluable
support in every way imaginable. I want to convey a loving thank you to my
special friend, Abdoulaye Kaba, for his support during the writing of this
dissertation. Others have provided valuable support, insight, friendship
and shoulders over the last years including Sonja Jonas, Clayton Clark, the
Makaveli Gainesville Tennis Crew, and the Black Graduate Student
Organization.
Finally and most importantly, I would like to give praise to the
Creator for making it all possible.
TABLE OF CONTENTS
page
ACKNOWLEDGMENTS iv
LIST OF TABLES ix
LIST OF FIGURES xii
KEY TO SYMBOLS xviii
ABSTRACT xix
CHAPTERS
1 INTRODUCTION 1
Research Significance 1
Theory of Photochemical Water Treatment 4
Photocatalysis 5
Photosensitization 8
The Solar Resource 10
Research Objectives 12
2 REVIEW OF SOLAR BASED WATER TREATMENT 14
Physical Processes 15
Distillation Processes 15
Passive distillation 15
Active distillation 21
Pasteurization Processes 24
Photo Processes 27
Solar Disinfection 28
SODIS 28
Halosol 29
Photocatalysis 29
Photosensitization 30
Summary 32
VI
3 EXPERIMENTAL DESIGN AND METHODS 34
Choice of Experimental Parameters 34
Contaminants 35
Catalyst Choice 35
Choice of Photosensitizer 37
Reactor Design 39
pH 43
Catalyst/Sensitizer Concentration 44
Laboratory Experimental Design 45
Materials and Methods 46
Reaction Vessels 46
Bacterial Inoculation 47
Reactor Chamber 49
Photocatalysis Reactor Setup 49
Photocatalysis Sampling and Analysis 50
Photosensitization Reactor Setup 51
Photosensitization Sampling and Analysis 52
Combination Experimental Setup, Sampling and Analysis 52
Experiments for Confirmation of Previous Work with Bromacil 53
4 RESULTS AND DISCUSSION 54
Dye Photosensitization 54
General Comments About Experimental Data 56
Statistical Treatment of the Data 58
Presentation of Results and Identification of General Trends 62
Data Analysis by ANOM 81
Effect of Sunlight 82
Effect of pH 86
Effect of Dye Concentration 89
Effect of Initial Coliform Density 97
Reactor Efficacy 99
Summary 101
Photocatalysis with Titanium Dioxide 102
General Comments About Experimental Data 104
Statistical Treatment of the Data 105
Presentation of Results and Identification of General Trends 105
Data Analysis by ANOM 112
Effect of Light 113
Effect of pH 117
Effect of Ti0 2 Concentration 120
Multiple Parameter Effects 128
Effect of Initial Colony Density on Disinfection 129
Other Effects 131
Photocatalysis vs. Air Stripping 132
Summary 134
Ti0 2 Photocatalysis Combined With Methylene Blue 135
General Comments About Experimental Data 136
vn
Statistical Treatment of the Data 137
Disinfection 137
Detoxification 142
Summary 152
Kinetic Considerations 152
Detoxification 152
Disinfection 154
General Summary of Results 157
5 SUMMARY AND CONCLUSIONS 159
Summary 159
Process Efficacy Comparison for Simultaneous Treatment 159
Drinking Water Quality 160
Conclusions 160
Recommendations for Future Work 161
REFERENCES 163
APPENDICES
A EXPERIMENTAL DATA 176
B LIGHT MEASUREMENT 260
BIOGRAPHICAL SKETCH 269
vm
LIST OF TABLES
Table page
1-1. Spectral Distribution of Solar Radiation 11
2-1. Examples of Photocatalytic Treatment of Water and Wastewater .... 30
2-2. Examples of Photocatalytic Treatment of Water and Wastewater .... 31
2-3. Summary of Photosensitized Treatment of Water and Wastewater. . 32
3-1. Photostability of Semiconductor Oxides Tested by Carey and Oliver
(1980) 37
3-2. Order of Effectiveness of Dyes at 10" 4 M Concentration on E. Coli
After 24 Hours Exposure to Light at Room Temperature 40
3-3. Design for Ti0 2 Photocatalytic Lab Experiments 46
3-4. Design for Photosensitization Lab Experiments 46
3-5. Design for Combination Lab Experiments 46
4-1. Insolation Measurements from Dye Sensitization Experiments 55
4-2. Descriptive Statistics of Measured Data for all Experiments 56
4-3. Average Standard Deviations for all Dye Photosensitization
Experiments 57
4-4. Mean Fractional Survival (± 31%) of E. coli @ t= 30 minutes in MB
Experiments 59
4-5. Mean Fractional Survival (±25%) of E. coli in MB Experiments 65
4-6. Mean Fractional Survival (±13%) of E. coli in RB Experiments 68
4-7. Benzene (±51) and Toluene (±29) Concentrations (ppb) in MB
Experiments 70
4-8. Benzene (± 46) and Toluene (± 36) Concentrations (ppb) in RB
Experiments 70
IX
4-9. Normalized Benzene (±0.09) and Toluene (± 0.11) Concentration in
MB Experiments 76
4-10. Normalized Benzene (±0.06) and Toluene (±0.07) Concentration in RB
Experiments 77
4-11. Calculated ANOM Values for Dye Photosensitized Disinfection 82
4-12. Sunlight Subgroup Averages for Dye Photosensitized Disinfection;
Values are Fractional Survival of E. coli 83
4-13. pH Subgroup Averages for Dye Photosensitized Disinfection. Values
are Fractional Survival of E. coli 86
4-14. Dye Concentration Subgroup Averages in Disinfection Experiments.
Values are Fractional Survival of E. Coli 90
4-15. Mean Fractional Survival of Bacteria in Ti0 2 Experiments 107
4-16. Mean Concentration of BTEX (ppb) in Ti0 2 Experiments 108
4-17. Calculated ANOM Values for Ti0 2 Photocatalysis 113
4-18. UV Light Subgroup Averages for Ti0 2 Photocatalysis. Values are
Fractional Survival of Bacteria and Normalized Chemical
Concentration 114
4-19. pH Subgroup Averages for Ti0 2 Photocatalysis. Values are
Fractional Survival of Bacteria and Normalized Chemical
Concentration 117
4-20. Ti0 2 Concentration Subgroup Averages for Disinfection. Values are
Fractional Survival of Bacteria and Normalized Chemical
Concentration 121
4-21. Mean Values for Fractional Survival as a Function of Light, pH and
Ti0 2 Concentration at t=240 Minutes 128
2
4-22. Mean Normalized Benzene Concentration After 30 Minutes in TiO
Experiments 129
4-23. Descriptive Statistics for Initial Colony Density in Ti0 2 Experiments 130
4-24. Vapor Pressure Values for BTEX components 133
4-25. Measured Sunlight Intensity in Combination Experiments 136
4-26. Average Standard Deviations for all Combination Experiments 137
4-27. Mean Fractional Survival (±14.1%) of E. Coli in Combination
Experiments 139
4-28. Calculated ANOM Values for Combination Experiments 139
4-29. Sunlight Subgroup Averages for Combined Experiments. Values are
Fractional Survival of Bacteria and Normalized Chemical
Concentration 139
4-30. Photochemical Subgroup Averages for Combination Experiments;
Values are Fractional Survival of E. coli and Normalized
Chemical Concentration 140
4-31. Mean Concentration (ppb) of Benzene (±120) and Toluene (±199) in
Combination Experiments; Lf t A = 433-833 W/m 2 , I m A = 25-40
W/m 2 147
4-32. Experimental First - Order Rate Constants (min "') for TiO
2
Photocatalytic Experiments 153
4-33. Correlation Statistics for Least Squares Linear Regression of Kinetic
Data; Confidence Level is 95% 154
4-34. First Order Rate Constants for All Photochemical Disinfection
Experiments 157
4-35. Time to Complete Destruction by Photochemical Treatment 158
XI
LIST OF FIGURES
Fi gure page
1-1. Graphical Representation of the Generation of e - /h + Pairs and
Recombination by Photocatalytic Reaction on the Surface of
aSemiconductor Particle 7
2-1. Conventional Passive Solar Basin Still 17
2-2. Schematic of Flash Distillation Using Solar Collector 22
3-1. Ti0 2 Reaction Vessel 47
3-2. Photosensitization Reaction Vessel 48
3-3. Graphical Representation of Bacterial Inoculation 48
3-4. Ultraviolet Light and Dark Reactor Chamber 50
4-1. MB Destruction of E. coli in Sunlight; (a) pH =10, I av = 542-696 W/m
2
avg
(b) pH =7, I = 665-891 W/m 2 63
avg
4-2. Destruction of E. coli in sunlight with 1 mg/L MB; (a) pH =10, I =
542-696 W/m 2 and (b) pH 7, T = 665-891 W/m 2 64
avg
4-3. RB Destruction of E. coli in Sunlight; (a) pH = 7, T = 746-856 W/m
2
avg
(b) pH = 10, 1 = 715-775 W/m 2 67
avg
4-4. RB Destruction of E. coli at pH =7, 1 = 715-775 W/m 2 ; (a) 5 mg/L RB
and (b) 10 mg/L RB 68
4-5. Benzene Concentration as a Function of Time and MB Concentration
in Sunlight; (a) pH=10, T = 542-696 W/m 2 (b) pH=7, T = 665-891
W/m 2 g 72
4-6. Toluene Concentration as a Function of Time and MB Concentration
in Sunlight; (a) pH =10, T = 542-696 W/m 2 (b) pH=7, 1 = 665-891
W/m 2 .* 73
4-7. Benzene Concentration as a Function of Time and RB Concentration
in Sunlight; (a) pH =10, T = 715-775 W/m 2 (b) pH=7, T = 746-856
W/m 2 Z 74
xn
4-8. Toluene Concentration as a Function of Time and RB Concentration
in Sunlight; (a) pH =10, I ave = 715-775 W/m 2 (b) pH=7, I ave = 746-856
W/m 2 75
4-9. Normalized Benzene Concentration in Sunlight with 0.1 mg/L MB,
(a) pH =10, I avg = 542-696 W/m 2 (b) pH=7, I avg = 665-891 W/m 2 78
4-10. Normalized Toluene Concentration in Sunlight with 0.1 mg/L MB;
(a) pH =10, I avg = 542-696 W/m 2 (b) pH=7, I avg = 665-891 W/m 2 79
4-11. Normalized Benzene Concentration in Sunlight with 0.1 mg/L RB, (a)
pH =10, I avg = 715-775 W/m 2 (b) pH=7, I avg = 746-856 W/m 2 80
4-12. Normalized Toluene Concentration in Sunlight with 0.1 mg/L RB, (a)
pH =10, I avg = 715-775 W/m 2 (b) pH=7, I avg = 746-856 W/m 2 81
4-13. Significance of Sunlight, Based on ANOM, in MB Experiments (a) 5
Minutes (b) 15 Minutes (c) 30 Minutes 84
4-14. Significance of Sunlight, Based on ANOM, in RB Experiments; (a) 5
Minutes (b) 15 Mintues (c) 30 Minutes 85
4-15. Significance of pH, Based on ANOM, in MB Experiments; (a) 5
Minutes (b) 15 Minutes (c) 30 Minutes 87
4-16. Significance of pH, Based on ANOM, in RB Experiments; (a) 5
Mintues (b) 15 Minutes (c) 30 Minutes 88
4-17. Statistical Significance of MB Concentration, Based on ANOM, on
Disinfection in Sunlight; (a) 5 Minutes (b) 15 Minutes (c) 30
Minutes 91
4-18. Statistical Significance of RB Concentration, Based on ANOM, on
Disinfection in Sunlight; (a) 5 Minutes (b) 15 Minutes (c) 30
Minutes 92
4-19. Comparison of Disinfection Efficacy of Control and 0.1 mg/ L MB in
Sunlight at 5 minutes, Based on ANOM 93
4-20. Comparison of Disinfection Efficacy of Control and 1 mg/L MB in
Sunlight at 5 minutes, Based on ANOM 94
4-21. Comparison of Disinfection Efficacy of Control and 5 mg/L MB in
Sunlight at 5 minutes, Based on ANOM 94
4-22. Comparison of Disinfection Efficacy of Control and 10 mg/L MB in
Sunlight at 5 minutes, Based on ANOM 95
4-23. Comparison of Disinfection Efficacy of 0.1 mg/ L and 10 mg/L MB in
Sunlight at 5 minutes, Based on ANOM 95
xm
4-24. Comparison of Disinfection Efficacy of 1 rag/ L and 10 mg/L MB in
Sunlight at 5 minutes, Based on ANOM 96
4-25. Comparison of Disinfection Efficacy of 5 mg/ L and 10 mg/L MB in
Sunlight at 5 minutes, Based on ANOM 96
4-26. Fractional Survival of E. coli in sunlight at t=30 minutes as a
Function of MB Concentration; Bars are One Standard Deviation
97
4-27. Least Squares Regression of Natural Logarithm of Fractional
Survival of E. coli as a Function of MB Concentration at t=5
Minutes 98
4-28. Initial Colony Count vs. Fractional Survival of E. coli at t=60 Minutes
for MB Experiments 98
4-29. Initial Colony Count vs. Fractional Survival of E. coli at t=30 Minutes
in RB Experiments 99
4-30. Ti0 2 Photocatalytic Disinfection in UV Light (29 W/m 2 ); Error Bars
are One Standard Deviation; (a) pH = 4 (b) pH = 7 106
4-31. Destruction of Benzene in Reactors 3 and 4 as a Function of Time;
Reactors Contained 0.01% Ti0 2 and were Irradiated for 60
minutes under UV Lamps (29 W/m 2 ) 110
4-32. Benzene Concentration in UV Light (29 W/m 2 ) as a Function of Time
and Ti0 2 Concentration; Error Bars are One Standard Deviation,
(a) pH =4, (b) pH = 7 110
4-33. Toluene Concentration in UV Light (29 W/m 2 ) as a Function of Time
and Ti0 2 Concentration; Error Bars are One Standard Deviation,
(a) pH =4, (b) pH = 7 Ill
4-34. m&p Xylene Concentration in UV Light (29 W/m 2 ) as a Function of
Time and Ti0 2 Concentration; Error Bars are One Standard
Deviation, (a) pH =4, (b) pH = 7 112
4-35. Significance of UV Light (29 W/m 2 ), Based on ANOM, on Bacteria in
Ti0 2 Experiments at 120 Minutes 115
4-36. Significance of UV Light (29 W/m 2 ), Based on ANOM, on Benzene in
Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes 115
4-37. Significance of UV Light (29 W/m 2 ), Based on ANOM, on Toluene in
Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes 116
4-38. Effect of UV Light (29 W/m 2 ) on Fractional Survival of Bacteria in All
Reactors in Ti0 2 Experiments; Bars are One Standard Deviationll6
xiv
4-39. Significance of pH, Based on ANOM, to Bacteria Destruction in Ti0 2
Experiments at 120 Minutes 118
4-40. Significance of pH, Based on ANOM, to Benzene Destruction in Ti0 2
Experiments (a) 30 Minutes (b) 60 Minutes 119
4-41. Significance of pH, Based on ANOM, to Toluene Destruction in Ti0 2
Experiments (a) 30 Minutes (b) 60 Minutes 120
4-42. Significance of Ti0 2 Concentration, Based on ANOM, on Bacteria in
Photocatalysis Experiments at 120 Minutes 121
4-43. Significance of Ti0 2 Concentration, Based on ANOM, on Benzene in
Photocatalysis Experiments; (a) 30 Minutes (b) 60 Minutes 122
4-44. Significance of Ti0 2 Concentration, Based on ANOM, on Toluene in
Photocatalysis Experiments; (a) 30 Minutes (b) 60 Minutes 123
4-45. Comparison of Control vs. 0.01% Ti0 2 on Photocatalytic Disinfection
at 120 Minutes, Based on ANOM 124
4-46. Comparison of Control vs. 0.05% Ti0 2 on Photocatalytic Disinfection
at 120 Minutes, Based on ANOM 124
4-47. Comparison of Control vs. 0.10% Ti0 2 on Photocatalytic Disinfection
at 120 Minutes, Based on ANOM 125
4-48. Comparison of 0.01% vs. 0.05% Ti0 2 on Photocatalytic Disinfection at
120 Minutes, Based on ANOM 125
4-49. Comparison of Control vs. 0.01% Ti0 2 on Photocatalytic Destruction of
Benzene at 60 Minutes, Based on ANOM 126
4-50. Comparison of Control vs. 0.05% Ti0 2 on Photocatalytic Destruction of
Benzene at 60 Minutes, Based on ANOM 126
4-51. Comparison of Control vs. 0.10% Ti0 2 on Photocatalytic Destruction of
Benzene at 60 Minutes, Based on ANOM 127
4-52. Comparison of 0.01% vs. 0.05% Ti0 2 on Photocatalytic Destruction of
Benzene at 60 Minutes, Based on ANOM 127
4-53. Fractional Survival of Bacteria as a Function of UV Light (29 W/m 2 )
and pH in Ti0 2 Experiments; Bars are One Standard Deviation
130
4-54. Effect of UV Light (29 W/m 2 ) and pH on the Destruction of Benzene in
Ti0 2 Experiments; Bars are One Standard Deviation 130
4-55. Initial Colony Count vs. Fractional Survival of Bacteria at t=120
Minutes for Ti0 2 Photocatalysis 131
xv
4-56. Normalized Concentrations of BTEX Components in pH 7 Dark
Experiments with 0.01% Ti0 2 133
4-57. Normalized Concentrations of BTEX Components in pH 4 Dark
Experiments with 0.01% Ti0 2 134
4-58. Destruction of E. coli in Sunlight (I T()t Avg = 433-853 W/m 2 , I w Avg = 25-40
W/m 2 ) in Combination Experiments 138
4-59. Significance of Sunlight (I Tot Avg = 433-853 W/m 2 , I uv _ Avg = 25-40 W/m 2 )
on E. coli Destruction, Based on ANOM, in Combination
Experiments; (a) 5 Minutes (b) 15 Minutes (c) 30 Minutes 141
4-60. Significance of Photochemical on E. coli Destruction, Based on
ANOM, in Combination Experiments; (a) 5 Minutes (b) 15
Minutes (c) 30 Minutes 143
4-61. Significance of Ti0 2 vs MB on E. coli Destruction, Based on ANOM, in
Combination Experiments; (a) 5 Minutes (b) 15 Miiues (c) 30
Minutes 144
4-62. Significance of Ti0 2 vs Both on E. coli Destruction, Based on ANOM,
in Combination Experiment; (a) 5 Minutes (b) 15 Minutes (c) 30
Minutes 145
4-63. Significance of MB vs Both on E. coli Destruction, Based on ANOM,
in Combination Experiments; (a) 5 Minutes (b) 15 Minutes (c) 30
Minutes 146
4-64. Normalized Concentration as a Function of Time in Combination
Experiments. L^ Avg = 433-833 W/m 2 , I uv Avg = 25-40 W/m 2 ; (a)
Benzene (b) Toluene 147
4-65. Significance of Photochemical on Benzene Destruction, Based on
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120
Minutes 148
4-66. Significance of Photochemical on Toluene Destruction, Based on
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120
Minutes 149
4-67. Significance of Ti0 2 vs Both on Benzene Destruction, Based on
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120
Minutes 150
4-68. Significance of Ti0 2 vs Both on Toluene Destruction, Based on
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120
Minutes 151
xvi
4-69. Least Squares Linear Regression of First Order Rate Equation for
Disinfection in UV Light (29 W/m 2 ) with 0.05% Ti0 2 and pH = 4; r 2
= 0.90, p-value = 0.0025 155
4-70. Least Squares Linear Regression of First Order Rate Equation for
Disinfection in UV Light (29 W/m 2 ) with 0.10% Ti0 2 and pH = 7; r 2
= 0.55, p-value = 0.019 155
4-71. Least Squares Linear Regression of First Order Rate Equation for
Disinfection in Sunlight (715-775 W/m 2 ) with no photochemical
and pH = 10; r 2 = 0.99, p-value = 0.0001 156
4-72. Least Squares Linear Regression of First Order Rate Equation for
Disinfection in Sunlight (746-856 W/m 2 ) with 1 mg/L RB and pH =
7; r 2 = 0.95, p-value = 0.0003 156
xvn
KEY TO SYMBOLS
\ Wavelength, nm
h Planck's constant, 6.625 x 10 J4 Js
c Speed of light, 3.0 x 10 10 cm/s
e Band gap energy, ev
hv Li g ht energy
n + Positive hole in the valence band
e - Electron
iX* Excited singlet state of component X
3x* Excited triplet state of component X
X* Excited state of component X
! X Singlet state of component X
3x Triplet state of component X
R Hydrocarbon group
I sc Solar constant
C t Concentration at time, t
N t Colony density at time, t
I Insolation, W/m 2
s Standard Deviation
X Grand Average of all Data in ANOM
X Subgroup Average for ANOM
s Average standard deviation
r Average Range
H ANOM Critical Value
v degrees of freedom
d 2 2 bias correction factor for ANOM
a significance factor
xvin
Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
SOLAR PHOTOCHEMICAL TECHNOLOGY
FOR POTABLE WATER TREATMENT:
DISINFECTION AND DETOXIFICATION
By
Adrienne Teresa Cooper
August 1998
Chairperson: Thomas Crisman
Cochairperson: D. Yogi Goswami
Major Department: Environmental Engineering Sciences
Clean water is scarce in many countries, and the goal of universal
access to water and sanitation has not yet been achieved. Standard water
treatment techniques are often expensive both in capital investment and
operation and maintenance, particularly in lesser developed communities
where resources are scarce.
Solar photochemistry has shown promise as an appropriate
alternative technology for treatment of water, and provides potential for
simultaneous disinfection and destruction of organic chemicals. The need
for simultaneous treatment arises when conditions of contamination of
source water, such as ground water, occurs. Potential sources of
contamination are industrial and agricultural runoff or leakage of
underground storage tanks (gasoline) and sewerage lines.
xix
In a series of bench scale experiments, three photochemical
technologies, Ti0 2 photocatalysis, dye photosensitization and a combination
of dye photosensitization and Ti0 2 photocatalysis, were evaluated for their
efficacy for simultaneous removal of coliform bacteria and aromatic
hydrocarbons in drinking water under a variety of pH and photochemical
concentration conditions.
Series of 100 ml and 500 ml reactors, containing various
concentrations of Ti0 2 , and two pH levels (4 and 7), were inoculated with
mixed bacteria species, benzene, toluene, and xylene, and illuminated
under ultraviolet light for several hours. Under most conditions both the
chemical and bacteriological contaminants were destroyed within an hour.
In photosensitization experiments, the 500 ml reactors were charged
with several concentrations of rose bengal or methylene blue and neutral,
pH 7, or basic, pH 10, water. After inoculation with Escherichia coli,
benzene and toluene, the reactors were illuminated for four hours in
sunlight. In all cases, the water was disinfected within one hour; however,
destruction of the chemical contaminants did not occur.
The 500 ml hybrid reactors, loaded with 0.01% Ti0 2 and/or 5 mg/L
methylene blue, were also illuminated in sunlight. The inoculations of
Escherichia coli, benzene, and toluene were completely destroyed after two
hours in all of the reactors which contained Ti0 2 ; however, the presence of
methylene blue inhibited the reaction.
xx
CHAPTER 1
INTRODUCTION
Research Significance
Clean and safe water is a requirement for healthy living and
development. While concerns with most water related diseases have been
virtually eliminated in most developed regions, such as Western Europe
and North America, diseases related to either the quantity or quality of
water supply are still a major problem in other parts of the world
In 1977 Stein reported that 25,000 deaths occurred daily from water
borne diseases. In an effort to reduce these deaths, the United Nations
declared the ten year period from 1981 to 1990 the International Drinking
Water Supply and Sanitation Decade. The goal of the decade was to provide
universal access to safe water and sanitation. While many advances were
made during this period to increase the supply of safe drinking water for
the global human population, universal access has yet to be achieved.
According to World Health Organization (WHO) estimates, as of 1990, 18%
of urban populations and 36% of rural populations (approximately 1.23
billion people) are still without access to safe drinking water supplies
(Christmas 1990). An inexpensive supply of clean water is one of the most
pressing public health issues facing developing communities.
Over 10 million deaths result from more than 250 million new cases
of water borne diseases yearly (Hazen and Toranzos 1990). During 1993
there were 272,500 reported cases of cholera in Sub-Saharan Africa and
Latin America, with death rates of 3% and 1%, respectively. In 1994 WHO
reported a decrease in the availability of clean water in several countries of
Sub-Saharan Africa. Their estimates, based on the continuation of current
trends, suggest that by the year 2025, the supply of renewable fresh water
per person in the worst drought-affected countries of the continent will
represent 15% of the 1955 values (WHO 1994). In many developing
communities, water related infections caused by poor biological drinking
water quality or lack of water supply are the most urgent public health
issues. The water related infections are acute, tending to act quickly,
causing illness and sometimes death. However, the chemical quality of
water is also of growing concern.
In the 1970s it was discovered that disinfection by chlorination of
water containing humic substances generates chloroform and other
trihalomethanes (THMs). THMs are known animal carcinogens (Clark
1992; Glaze et al. 1993a; Moser 1992; Packham 1990; Stevens et al. 1989),
raising concerns about chemical disinfection by-products and their
toxicological effects on the population.
Rachel Carson (1962) brought the issue of pesticide contamination of
water and soil to the forefront. The growth of industry and the prevalence
of agricultural pesticides and fertilizers s cause concern for the effect of
these discharges on the chemical quality of water. An increase in
motorized transportation leads to contaminated runoff and the potential for
leakage of benzene, toluene and other aromatic hydrocarbons. These
activities can have a severe impact on drinking water sources. The effect of
chemical contaminants on public health is more often chronic, building
over time and causing long term illness (Droste and McJunkin 1982).
Standard water treatment techniques are very well defined in the
United States and other developed countries. However, due to differences in
economics and infrastructure, these treatments are not necessarily readily
transferable from the developed to the developing world, including some
lesser developed areas of developed nations. The operational and capital
costs for this technology are often too expensive for developing
communities.
The development of community appropriate technology for treatment
of drinking water is critical if universal access to a safe water supply is to
be achieved. Utilization of available natural resources, where feasible,
provides a greater opportunity for a sustainable drinking water supply.
This requires innovative and creative technology.
While no one technology can meet all of the needs of a community,
solar photochemical oxidation holds promise as a viable alternative to
standard, more expensive methods. The efficacy of the photocatalytic
reaction has been demonstrated for biological contaminants (Block et al.
1997; Ireland et al. 1993) and chemical contaminants (Blake 1994; Legrini
et al. 1993). Therefore, it is reasonable to expect that the simultaneous
destruction of both chemical and biological contaminants can be
accomplished, although it has not been reported. While some
investigations of simultaneous disinfection and detoxification with dye
photosensitization have been undertaken (Acher 1984; Acher and
Rosenthal 1977; Eisenberg et al. 1987a; Eisenberg et al. 1986), these
processes have not been optimized, nor have they been compared directly
with photocatalysis. The success of previous studies indicates that solar
photochemical technology, when properly integrated with conventional
treatment, has the potential to address the technical issues of water
treatment facing a community.
Use of solar photochemical technology for water treatment has the
potential to provide a solution which is technically, economically and
socially acceptable, manifested by the following potential benefits:
• The use of the sun as a primary driver results in a renewable and
essentially free source of energy for the reaction
• Photochemical oxidation results in complete destruction of
pollutants, which is preferable to dissipation, concentration or
change of form
• Since very small quantities of sensitizer or catalyst are required,
and little if any external energy besides the sun, the technology
has the potential for low capital and maintenance costs
• The process is easily adaptable to a small scale, and therefore,
suitable for rural and suburban communities
Theory of Photochemical Water Treatment
Photochemical water treatment is an oxidation process which
involves the use of a chemical as a catalyst or sensitizer for indirect
photolysis of a contaminant within the water. When exposed to light of the
appropriate wavelength, which is governed by the photochemical used, the
photosensitizer or photocatalyst generates a reactive species, an hydroxyl or
peroxy radical, which subsequently reacts with the contaminant species
(Ollis et al. 1989; Schiavello 1988; Teichner and Formenti 1985). This
indirect process opens a much wider range of contaminants to destruction
by photochemical means than would be available using only direct
photolysis. The photochemical water treatment processes evaluated herein
are photocatalysis, photosensitization and a combination of the two. The
distinction between photocatalysis and photosensitization is based on the
nature of the photochemical used.
Photocatalysis
Photocatalysis, or photocatalytic oxidation, for water treatment
applications refers to a heterogeneous oxidation reaction involving solid
semiconductor surfaces. The reaction occurs via the irradiation of a
semiconductor catalyst, such as titanium dioxide (Ti0 2 ), zinc oxide (ZnO),
or cadmium sulfide (CdS), with visible or ultraviolet (UV) light. The
reaction is possible because of the structure of the semiconductor. The
optical bandgap of a semiconductor is an area devoid of energy levels,
between the highest occupied energy band, the valence band, and the lowest
unoccupied energy band, the conduction band. When a semiconductor
absorbs light with energy greater than the energy of the semiconductor's
optical band gap, photoexcitation results (Bahnemann et al. 1991; Mills et
al. 1993). For example, since Ti0 2 has an optical band gap energy of 3.2 eV,
absorption occurs with light of wavelengths less than 388 nm, ultraviolet
light, as indicated by equation 1-1 (Zhang et al. 1994b).
x = ^
^(6.625xl(r 34 Js)(3.0xl0 10 cm /p
3.2eV
x| leV 5 I
ll.6xl(T 19 J '
J
The resulting excitation leads to the promotion of excess free
electrons, e~, to the conduction band, leaving positive "holes," h + , in the
valence band, referred to as electron/hole (e~/h + ) pairs. Equation 1-2
describes this process (Carey and Oliver 1980; Oliver and Carey 1986). The
electrons and holes are highly energetic and very mobile (Turchi et al.
1989).
Ti0 2 + hv =* h + + e~ ( 1-2 )
There are two paths that the e~/h + pairs can take. They can either
recombine and deactivate, or migrate to the surface of the semiconductor
and react with surface species as shown in equations 1-3 to 1-5. Figure 1-1
is a graphical representation of this process for a single semiconductor
particle.
OH' + h + -> OH" ( 1-3 )
H 2 (ads) + h + -> OH" + H + ( 1-4 )
e~ + 2 -> HO; - ( 1-5 )
If reactions 1-3 to 1-5 take place, reactive species are formed, which
in turn are able to oxidize organic contaminants in the water. The less
recombination which takes place, the more efficient the semiconductor is
as a photocatalyst.
The peroxy radical, HO^, disproportionates further to form more
hydroxyl radicals, OH', which combine with organic substrate to form
oxidation products as shown in reaction 1-6 (Blake et al. 1991; Ireland et al.
1993; Oliver and Carey 1986). If enough catalyst and light are present, a
OH' + substrate — > oxidation products
(1-6)
pseudo chain reaction occurs resulting in complete mineralization of
organics. It is thought that the process for the destruction of biological
substrate is very similar, with the oxidation of proteins, lipids or nucleic
acids resulting in inhibition of respiration or growth of the microorganism
(von Sonntag 1987).
hv >
Reduction
Electron Energy
Adsorption
of6 2
Adsorption
ofH 2
Oxidation
Figure 1-1. Graphical Representation of the Generation of e~/h + Pairs and
Recombination by Photocatalytic Reaction on the Surface of a
Semiconductor Particle; After Bahnemann et al. (1991) and
Tseng and Huang (1990)
8
Photosensitization
Sensitized photolysis, also referred to as photosensitization or
photodynamic action, is another method of indirect photolysis very similar
to photocatalytic oxidation. In photosensitization, energy is transferred
from a photochemically excited molecule to an acceptor. The sensitizer (S),
often a dye, absorbs light and is photochemically excited to a higher energy
state. This process may offer an advantage over the photocatalytic process
because the sensitizers can absorb light in the visible spectrum, allowing
for use of a greater percentage of available sunlight. The reaction proceeds
via the triplet excited state, owing to its longer lifetime relative to the singlet
excited state (Foote 1968; Larson et al. 1989) as shown in equation 1-7.
S + hv -» "S* (excited singlet) -» 3 S* (excited triplet) ( 1-7 )
The excited sensitizer (S*) then transfers some of its excess energy to
an acceptor, forming a reactive, transient form of oxygen, singlet oxygen,
l 2 (Larson and Weber 1994). Acceptors can be either organic material
(OM) or dissolved inorganic species such as molecular oxygen, 2 . The
intermediate reactive species produced from the reaction of the triplet
sensitizer with organic material subsequently reacts with atmospheric
oxygen under aerobic conditions (equation 1-8).
3 S* + OM -> transient specia + 2 -> oxidation products + S ( 1-8 )
When the S* transfers its excess energy to molecular oxygen instead
of OM, the oxygen molecule changes from its ground electronic state, the
triplet state ( 3 Z g 2 ), to the excited singlet state, l 2 . The organic matter is
then oxidized by the '0 2 to form oxidation products. Acher and Rosenthal
(1977) described the mechanism by reactions 1-9 and 1-10:
3 S* + :, X K 2 -^ S + '0 2 ( 1-9 )
'0 2 + OM -» oxidation products ( 1-10 )
When '0 2 combines with unsaturated organic compounds (UC), it
yields free radicals which readily combine with nucleic acids, lipids and
proteins for destruction of microorganisms as demonstrated by reactions 1-
11 to 1-13 (Acher and Rosenthal 1977).
'0 2 + UC -> ROOR -* RO* ( 1-11 )
RO'+RH^ROH + R* (1-12)
R' # + 2 ->ROO\etc. (1-13)
The wavelength of light absorption is specific for each sensitizer.
Methylene blue and rose bengal are widely used dye sensitizers which
absorb in the visible region at X. max 668 nm and X. max 549 nm, respectively
(Acher and Juven 1977).
Ideal sensitizers are defined as those compounds which exhibit the
following criteria (Acher and Rosenthal 1977):
• induce reactions with visible light,
• are chemically stable during radiation or degrade to a sensitizing
species,
• are free of reactive functional groups,
10
• have good light absorption capacity, and
• are soluble in water but easy to remove.
Compounds which exhibit these qualities most efficiently are dyes,
such as fluorescein and phenothiazine derivatives, flavins, certain
porphyrins and polycyclic aromatic hydrocarbons (Foote 1968). For the
purposes of water treatment, the latter two are too toxic; however, the
others are acceptable. The sensitizers which have shown the most promise
for both disinfection and detoxification, and which were evaluated for this
research, are methylene blue and rose bengal. These dyes have been found
to be relatively easily removed by precipitation with bentonite clay (Acher
and Rosenthal 1977).
The Solar Resource
The sun can be modeled as a blackbody with a steady-state
temperature of 5800K, radiating approximately 6.416 x 10 7 W/m 2 from its
surface (Wieder 1992). The intensity of the sun's radiation on an object is
inversely related to the square of its distance from the sun (Hsieh 1986).
Since the distance of the earth from the sun varies throughout the year, the
amount of sunlight reaching the atmosphere of the earth is not constant.
However, a value termed the Solar constant, I sc , is the amount of solar
radiation reaching a surface normal to the rays of sun outside the earth's
atmosphere at a mean earth-sun distance of 1.5 x 10 11 m (Hsieh 1986).
Based on measurements, the established value of the Solar constant is 1377
W/m 2 (Randall and Bird 1989). Solar radiation reaching the atmosphere of
the earth emits energies of wavelengths from gamma to radio, with most of
11
it concentrated in the visible region. The spectral distribution of the solar
radiation outside the earth's atmosphere is given in Table 1-1.
Table 1-1. Spectral Distribution of Solar Radiation
Wavelength (jim)
0.00- 0.395 (gamma to ultraviolet)
0.40 - 0.70 (visible)
0.71 - 2.00 (near infrared)
2.00 - °° (infrared to radio)
Source: Thekaekara ( 1976)
■.-.-.-.-.-.-.-. -.-.-.-.-.-.-.-^.-.•.-.-.•.■.-.■.-.■.v
■.■:•:■:■:■:•••:•:•:•:■:•:•••:•:•:•:•>:
% of Total
8.24
38.15
45.61
6.51
■:v->>xo:-:-:-:-:-v.:.:-:.:ox-:-:-:-:-:-:->x-:^^
The amount of solar radiation, also referred to as insolation,
available at the earth's surface at a given time is dependent on the
prevailing climatic conditions, the level of atmospheric pollution and the
angle at which the sun strikes the surface (Hsieh 1986). Scattering and
absorption of radiation, due to the presence of ozone, gas molecules,
particulate matter and water vapor (including clouds), account for a
significant reduction in the solar radiation incident on the earth's surface
(Barry and Chorley 1992). The path length of the solar radiation in the
atmosphere, which changes with the time of day and latitude, determines
the amount of extinction of radiation by these parameters (Hsieh 1986).
Approximately 4-6% of the solar radiation reaching the earth's surface is in
the ultraviolet wavelength range (Goswami 1995). The remainder of
incident radiation is in the visible and near infrared range. Using
historical weather data the direct beam incident radiation for a given
location in space and time can be calculated with reasonable accuracy
(Randall and Bird 1989).
12
The photochemical oxidation process is governed by the absorption of
light within the wavelength of effectiveness of the catalyst or sensitizer
used. For the Ti0 2 photocatalytic process, the ultraviolet part of the
spectrum, wavelengths below about 390 nm, is the most critical (Goswami
1995). This process, therefore, is well suited for areas where cloudiness
prevails, as the ultraviolet light is often present both as scattered and direct
beam radiation.
Photosensitization works with visible light, which is the greater part
of direct beam incident radiation. The sensitizers evaluated in this work,
methylene blue and rose bengal, are most effective in the blue (~ 670 nm)
and red (~ 550 nm) ranges, respectively (Acher and Juven 1977).
Research Objectives
There exists a need for research, at all levels, tailored to address the
needs of smaller, and possibly lesser developed, communities. The direct
transfer of technology from one community to another is one of the
solutions. However, it cannot serve as a replacement for the development of
regional and community specific technology to solve regional and
community specific problems.
In order for this more localized technology development to occur,
however, the information base must be expanded. One primary method for
the appropriate expansion of the information base is the conduction of
research which is more focused on the needs specific to these communities.
The investigation of basic techniques, technologies and processes which
13
may differ from the mainstream is key to the provision of tools necessary for
the advancement and development of all communities.
The research reported herein is an effort to add some knowledge to
that information base, and addresses two key areas of photochemical
technology:
• simultaneous treatment of chemical and microbiological
pollutants,
• comparative efficacies of photosensitization, photocatalysis and
combined photosensitization and photocatalysis,
While the research reported herein is not a solution to the problem of
water supply, it is anticipated that the knowledge derived from this
research could be applied to accept or reject one option, photochemical
treatment, as a partial solution. In the process of creating a better reality,
the best that one can wish for is options and the information to adequately
evaluate those options.
CHAPTER 2
REVIEW OF SOLAR BASED WATER TREATMENT
The use of sunlight for water treatment is not a recent phenomenon.
Documented evidence for solar distillation systems exists as far back as
1551 when Arab alchemists used glass vessels and concave mirrors to
distill water (Malik et al. 1982). However, technologies for solar based water
treatment have changed dramatically in recent years. The development of
photochemical technologies have significantly expanded the application
potential for solar based water treatment processes. What follows is an
exploration of the various methods of water treatment which use solar
energy as the primary driver, and a review of the current state of related
research.
Solar based water treatment processes can be roughly categorized as
either physical or chemical. Physical processes are those processes which
use the sun as a source of heat energy. Distillation and heat pasteurization
fall into the physical process category. The chemical processes are those
which involve a chemical reaction either directly or indirectly induced by
light. These photolytic processes include ultraviolet disinfection and a
number of photochemical processes.
14
15
Physical Processes
Distillation Processes
The most studied solar based water treatment process is desalination
by distillation. Solar distillation involves the use of sunlight to evaporate
saline or brackish water for the purpose of collecting the desalinated
condensate. Two approaches have been taken in the development of solar
distillation units. The first, and more conventional, involves the direct
absorption of solar energy by saline water, called passive solar distillation.
The second, active solar distillation, is similar to a standard chemical
distillation process using sunlight as the heat energy source for indirect
heating of the water. In this type of unit, evaporation is in a centralized
facility (Malik et al. 1982; Rajvanshi 1979).
Passive distillation
Passive solar distillation is easily understood when compared to the
natural process of the hydrologic cycle. In the hydrologic cycle, the sun
provides energy which warms the water of the oceans and other large
water bodies, causing evaporation. Convective wind energy transports this
vapor into the atmosphere where it condenses and produces precipitation.
The precipitation either directly, as rain, or indirectly, as melted snow,
recharges fresh water sources: lakes, rivers, streams, underground
springs and groundwater aquifers.
The solar distillation process is a simulation of this process in
manufactured facilities. The sun warms the collected body of saline or
brackish water and causes evaporation. The water vapor is carried by
16
convective winds, induced by the appropriate construction, and, upon
cooling, the vapor condenses as pure distilled water.
The conventional design for passive distillation systems is the basin-
type solar still (Figure 2-1). The bottom surface of the basin is black to
enhance the absorption of radiation by the saline or brackish water,
supplied either continuously or batchwise (Malik et al. 1982; Rajvanshi
1979). The basin is covered with a transparent, air tight cover which slopes
downward to facilitate transport of the condensate as a thin film into a
collection trough (Malik et al. 1982; Rajvanshi 1979). Solar radiation
penetrates the cover, generally glass or plastic, and is absorbed by the
water, warming it to induce evaporation. The temperature differential
between the cover, which does not absorb much radiation, and the water
surface leads to air convection currents which move the water vapor to the
underside of the cover. The cool temperatures of the basin cover, relative to
the water temperature, cause condensation, and the water forms a thin
film which is collected via troughs. Basin stills can be either shallow or
deep, depending upon the design and operational requirements. Shallow
basins stills have water depths ranging from 1.25 cm (0.5 in) to 5 cm ( 2 in)
and deep basin still water depths range anywhere from over 5 cm (2 in) up
to 91 cm (3 ft) (Rajvanshi 1979).
The first modern commercial solar still was installed in 1872 in the
northern part of Chile, designed by Swedish engineer Carlos Wilson. The
glass covered basin type solar still was 4700 m 2 and operated for many years
treating feedwater with a salinity of 140,000 ppm (Howe and Tliemat 1977;
Malik et al. 1982). Work conducted at the University of California's
17
Engineering Field Station in Richmond, California, concentrated on
reducing capital costs and improving efficiency of the basin still by
changing the geometric configuration. Designs tested included a circular
still, several trough type stills with rounded or v-shape bottoms and
stairstepped stills. The general conclusion of this work was that the basin
type solar stills were not economically competitive in any of the tested
configurations (Howe and Tliemat 1977).
Solar
Radiation
Glass Cover
Collection
Troug
Saline Water In
Basin Water
Condensate
Film
convective
Winds
Distillate
Out
Blackened Basin Bottom
Brine Out
Figure 2-1. Conventional Passive Solar Basin Still; After Malik et al. 1982
and Rajvanshi (1979)
At the University of Florida's Solar Energy and Energy Conversion
Laboratory, Rajvanshi (1979) evaluated the efficacy of dyes as a means of
increasing the efficiency of solar distillation. Using deep basin stills he
added dye to saline water to increase radiation absorption and alter the heat
18
transfer rate. Three dyes, black napthylamine, red carmoisine, and a dark
green mixture were used. The water treated with up to 500 ppm dye had an
increased output of as much as 29% on clear days, however, no increase in
output was observed with the dyes on completely cloudy days. Both the red
and green dyes degraded when exposed to sunlight, however, the black dye,
which also exhibited the largest increase in evaporation rate, did not visibly
degrade with exposure to sunlight.
Other research has focused on developing and improving the
conventional basin type passive still. What emerged was the tilted tray solar
still, wick solar stills, and double basin stills (Al-Karaghouli and Minasian
1995; Higazy 1995; Howe and Tliemat 1977; Malik et al. 1982).
The tilted tray solar still is a variation of the basin type solar still in
which the basin is broken into a series of narrow strips arranged like steps.
Each strip is on a different elevation, bringing the water surface much
closer to the transparent cover, and increasing the operating efficiency.
Generally these types of stills have very shallow basins. While the
efficiency is increased, so is the capital cost, making this type of still
infeasible for commercialization (Howe and Tliemat 1977).
Wick still designs utilize an absorbent material (wicking), usually
black to absorb radiation, as a facing on a glass covered inclined plane.
Saline water is introduced along the upper edge of the inclined plane and
trickles down saturating the wicking. The primary difficulty with this
design is an inability to maintain a uniformly wet surface (Howe and
Tliemat 1977).
19
Double basin stills utilize the latent heat of the condensing water
vapor, thereby increasing the daily yield over the conventional basin design.
The double basin still has two transparent covers. The inner glass cover
acts as a second, very shallow basin, with water running over it like a thin
film from a pipe in the center. The heat from the water condensing on the
underside of the lower basin cover is used to aid vaporization of the water
on the topside, which then condenses on the upper cover. The distilled
water is drained and collected from the underside of both transparent
covers (Malik et al. 1982).
During World War II Dr. Maria Telkes designed an inflated plastic
still for use with the life rafts of the United States armed forces (Howe and
Tliemat 1977). The design was similar to the basin still, however, it
utilized a saturated sponge as the absorption media, and the entire
assembly was designed to float on top of the water. Distillate was collected
in a bottle at the bottom of the unit. These types of stills were referred to as
floating sponge solar stills and reportedly over 200, 000 of them were
produced during the war (Howe and Tliemat 1977).
Higazy (1995) reported on the design and performance of a floating
sponge solar still for desalination of sea water. The still design was based
on the original design by Telkes. In Higazy's design water was pumped
into the bottom of the still and constituted the bottom layer. Above that layer
was a plastic sponge covered with a black cloth, which was where the
radiation was absorbed and then transferred by conduction to the sea water.
He examined two still designs, a single sloped cover which used mirrors to
increase the radiation absorption area and double sloped cover, evaluating
20
the parameters of insolation intensity, temperature and the sponge
properties (thickness and density). The primary improvement of this
system over Telke's was that the use of plastic parts eliminated the problem
of corrosion.
Higazy's experiments were conducted using tap water and it was not
indicated whether salts were added to simulate the saline environment
produced by sea water, although the physical and behavioral properties
were very similar. The design had no provisions for drainage of sea water
or periodic removal of the salts from the still and or the sponge, and
eventually problems might result from salt accumulation.
Al-Karaghouli and Minasian (1995) developed a new type of passive
solar still using a floating-wick and compared the still to conventional basin
solar still and the tilted wick solar still. They also introduced azimuth and
altitude tracking to increase the incident solar radiation on the still. The
floating wick still was a conventional basin type solar still which contained
a blackened jute wick floated on a polystyrene sheet. The unit floated no
more than 0.5 cm above the still water level. The benefit of the floating wick
still was due to the capillary action of the jute cloth, which was prepared in
a corrugated shape to restrict salt accumulation to the upper parts. The
stills used for comparison were made with the same materials and similar
style to the floating wick for direct comparison. The floating wick solar still
had a higher output than the other stills with which it was compared.
The use of a corrugated shape solved the problem of scale formation
and, due to the capillary action of jute cloth, the wick stayed uniformly
wet. Consequently, in the summer months the floating wick still had a
21
higher output, versus comparable performance with the wick still during
the cooler months. Tracking increased the output on all of the stills but was
particularly impressive with the floating wick still, almost doubling the
performance without tracking and having at least 30% higher output than
the conventional basin still with tracking (Al-Karaghouli and Minasian
1995).
Solar distillation technology is fairly well established and has proven
useful for small scale desalination of water. However, research has not
advanced to the point where large scale processes are economically
competitive with more conventional methods of distillation.
Active distillation
Active solar stills are those systems in which the sun's energy is
captured external to the distillation system, either as thermal energy or
photovoltaic electrical energy used to generate heat. In both cases the
generated heat is then applied to the distillation unit. They can operate in
conjunction with the conventional basin still, or they can be designed like a
conventional flash distillation unit. Figure 2-2 shows a standard schematic
for an active solar still which uses a solar collector and multistage flash
distillation.
Prasad and Tiwari (1996) conducted a thermal analysis of a
concentrator-assisted solar distillation unit to optimize the inclination of
the glass cover. They determined that the angle of inclination had an effect
on the yield of this active solar distillation system, with an increase in yield
which corresponded to an increase in the angle of inclination. For the
climatic conditions studied (Delhi, India, latitude 28° N, longitude 77° E) an
22
angle of 75° was found to be optimal. The increased angle also led to a
decrease in operating temperatures and evaporative heat losses.
Solar Radiation
^>
Of
u
3 <
* 5
B
m
( s.
r~^\
H
\f p IV
N/
CO
T\
?apor T
f N
■
— i
Heat
Exchanseh
fc
r/ t^*
V
Brine FlashChambers
Feed
Could o:
oi>jE Unit
Saline
Water '■
Figure 2-2. Schematic of Flash Distillation Using Solar Collector; After
Malik et al. (1982)
Farwati (1997) conducted a comparison of a multi-stage flash
distillation system using solar energy input with flat plate versus
compound parabolic collector (CPC) systems. The conditions used for
evaluation were monthly average climatic conditions for Benghazi, Libya.
Both collectors had an aperture area of one square meter. The compound
parabolic collector was able to achieve a higher water temperature for entry
into the flash distillation system (122°C vs 80°C) and a larger monthly
average daily output with maxima of 64.9 liters for the CPC and 43.7 liters
for the flat plate collector system in the month of August. Both systems
operated with auxiliary heaters. Using the solar collectors alone, the CPC
had a maximum monthly average daily distillate output of around 40 liters
and the flat plate collector one of about 25 liters.
Kumar and Tiwari (1996) compared performance of flat plate
collector solar distillation systems in several operating modes. They
23
examined the systems with and without flow over the glass cover, operating
in active versus passive mode and in double effect passive mode (i.e. second
glass cover with water flow over the cover closest to the basin). They found
that water flow over the glass cover gave the highest yield, as this decreased
the condensation surface temperature and utilized the latent heat of
condensation providing additional distillation. The system was a single
basin solar still made of fiber-reinforced plastic, coupled with a flat plate
collector and was really a hybrid of the passive and active system. The
double effect mode did not enhance performance because of the difficulty of
maintaining low and uniform flow rates over the glass cover. Tests were
run with 1 m 2 area of cover and collector. On average the active mode with
water flow yielded 7.5 liters per day, the passive mode yielded 2.2 liters per
day, and the active without water flow yielded 3.9 liters per day.
Sing and Tiwari (1993) evaluated and compared the yields and
thermal efficiencies of those types of solar stills recommended for rural or
urban applications The types of stills evaluated were: 1) passive single
basin, 2) passive double basin, 3) multiwick single basin, 4) multiwick
double basin, 5) active single basin and 6) active double basin. As
anticipated, the double basin stills outperformed the single basin
counterparts in both daily yield and thermal efficiency. Of the systems
studied, the active double basin had the highest yield while the multiwick
double basin had the best thermal efficiency. However, the use of the double
basin was not recommended with high salinity feedwater (> 20,000 ppm).
The multiwick single basin was suggested for moderate salinity (<1500
24
ppm) and the double basin designs were only recommended if technical
personnel were not readily available.
Pasteurization Processes
Pasteurization, or thermal disinfection, is the application of heat for
a specified time in order to destroy harmful microorganisms (Parker 1984).
The pasteurization process is best known for it's use in the food and
beverage industry, particularly for the pasteurization of milk. Recently,
this technology has been examined for it's use for drinking water. In order
to sterilize water by pasteurization, the water must be heated to a
temperature of 72°C (161°F) for a minimum of 15 seconds (Cheremisinoff et
al. 1981). Pasteurization can be obtained at lower temperatures, as low as
55 - 65°C (134 - 149°F); however, the required residence time increases
significantly as the temperature is reduced (Ciochetti and Metcalf 1984;
Joyce et al. 1996). The lower temperatures are attainable by solar heating.
One primary benefit of thermal disinfection over the photooxidation process
is that light penetration is not required, thereby making it effective in high
turbidity water.
Andreatta et al. (1994) reviewed the use of pasteurization devices in
the developing world with reference to several different styles of systems.
The solar box cooker, solar puddles and flow through systems similar to
solar hot water heaters have all been used as pasteurizers.
The solar box cooker used as a pasteurizer is the least expensive, but
also the most unreliable. A method for ensuring that the appropriate
temperature has been reached is required and sometimes difficult to verify.
25
Another drawback is that it is strictly a batch method, so the water is not
available throughout the day (Andreatta et al. 1994).
A flow through device can be manufactured using readily available
materials such as an automobile radiator thermostat valve and black
painted tubing. The design is a simple heat exchanger, and several design
variations have been tested. Flat configurations have been demonstrated to
be more effective than tubular varieties, although the tube exchanger may
be simpler to construct. The temperature control is very important, and the
design is critical in order to have the appropriate residence time. The
primary benefits of the flow through pasteurizer are the availability of
water throughout the day, easier control and ability to process larger
quantities of water (Andreatta et al. 1994).
The solar puddle is a low cost large area device. It resembles a solar
basin still in that there is a trough and a cover of clear plastic, however,
since the water is not saline, there is no need to separate the condensate
from the water in the puddle. For the puddle, determining that the
appropriate water temperature and residence time is reached is difficult
(Andreatta et al. 1994).
Ciochetti & Metcalf (1984) evaluated the use of a solar box cooker
(SBC) for pasteurization of water. They found that temperatures for milk
pasteurization (65°C) for several hours were sufficient to kill most
waterborne pathogens including viruses. Vertical temperature
differentials were found within containers, and the position of both the jug
in the SBC and the SBC itself had a significant effect on temperature and
consequently sterilization. Tests were conducted in northern California
26
and required temperatures for pasteurization were reached for
approximately six months of the year, from mid-March through mid-
September.
Joyce etal. (1996) investigated the thermal contribution of sunlight to
the inactivation of fecal coliforms with both onsite testing and laboratory
simulations. Their research was focused on the use of pasteurization for
household systems. Using transparent 2-liter plastic bottles, of the type
used for carbonated beverages, the water was heated to a temperature of
about 55 °C, the same temperature recorded for 2-liter bottles of water in full
sunshine in Kenya (latitude, 1°29'S; longitude, 36°38'E). Complete
disinfection was obtained after 7 hours at 55°C.
Burch and Thomas (1997) evaluated the feasibility of solar
pasteurization for water treatment in developing communities, comparing
it with other technologies traditionally employed in that arena. They
concluded that solar pasteurization, preceded by roughing filtration for
high turbidity water, was not economically competitive when compared
with slow sand filtration, chlorination, and UV disinfection. However, it
was the most effective of the four for a broad spectrum of microbiological
contaminants and had the lowest maintenance requirements. Flow
through solar pasteurization was slightly less costly than existing batch
processes, and the cost could be reduced more with the use of a thin-film
polymer system currently under study (Burch and Thomas 1997).
Solar pasteurization is not a feasible method for large water
purification systems, however, it shows clear promise for small remote
communities, household needs or emergency situations in areas with
27
several hours of sunshine throughout the day. Pasteurization has the
benefit of providing disinfection regardless of the turbidity of the water. One
major hurdle is the ineffectiveness on cloudy days, which may be
circumvented by having storage available and purifying larger quantities of
water on clear days for cloudy day use.
Photo Processes
Experiments on the effect of sunlight on microorganisms were
conducted as early as the late 19th century. Downes and Blount (1877)
observed the disappearance of turbidity, as an indication of the presence or
absence of microorganisms, from acidic urine placed in sunlight for
several hours. Since that time, much has been learned about the effect of
light, specifically ultraviolet radiation, on the inactivation of
microorganisms.
In the early 1900s direct photolysis by ultraviolet (UV) radiation was
used for disinfection of potable water (Wolfe 1990). While this method was
abandoned in favor of chlorination, problems with chlorine disinfection by-
products have encouraged researchers to take another look at UV. Recent
studies on the use of UV for drinking water have proven more successful
(Slade et al. 1986; Wolfe 1990). Direct photolysis, however, only affects those
species which can directly absorb light, primarily microorganisms.
Indirect photolysis, photosensitization or photocatalysis, provides
another alternative. When exposed to light of the appropriate wavelength,
the photosensitizer or photocatalyst generates a reactive species, such as a
hydroxyl radical or peroxy radical, which subsequently reacts with the
28
contaminant species. This opens a much wider range of contaminants to
destruction by photochemical means and creates the possibility of
simultaneous destruction of microbiological and chemical contaminants.
Solar Disinfection
Solar disinfection is direct photolysis by radiation from the ultraviolet
spectrum (wavelengths shorter than 390 nm) sometimes referred to as
photodynamic inactivation. Acra et al. 1990 have used sunlight for small
scale disinfection of drinking water by direct photolysis of microbiological
contaminants. Acra et al. (1990) postulated that a minimum solar UV-A
intensity of 17.8 W/m 2 was required for 99.9% inactivation of fecal coliform
based on field testing of solar disinfection reactors. The residence time
required to reach these levels of inactivation ranged from 90 minutes to 2.5
hours depending on the microorganism (Acra et al. 1990). The data
indicated that a longer residence time, achieved by recirculation, lower flow
rates, or increased reactor volume, could also lead to inactivation (Acra et
al. 1990). They found that bacterial destruction wsa exponential as a
function of solar UV-A intensity and time. The major problem encountered
was the growth of phytoplankton in the reactor (Acra et al. 1990).
In studies for the inactivation of Escherichia coli in sunlight, Shah et
al. (1996) found that the rate of inactivation was related to the initial colony
density. At very high initial densities of E. coli, inactivation was not
sufficient for provision of safe drinking water.
SQDIS
A hybrid technology which combined the benefits of UV disinfection
and heat pasteurization was proposed by Sommer et al. (1997). With the
29
SODIS reactors water was heated to a temperature of 50°C and subjected to
solar UV-A providing both thermal and UV disinfection. Complete
inactivation of fecal coliform in 2.5 hours was reported, even on completely
cloudy days. The hybrid technology was more effective on the partly cloudy
to completely overcast days when compared to pasteurization alone at 70°C.
Halosol
The halosol process is a combination of the use of halogens and
sunlight developed at the American University in Beirut, Lebanon in the
late 1970s to early 1980s. The process involves treatment with large doses of
sodium hypochlorite or iodine solutions followed by exposure to radiation.
The intended benefit is disinfection of small volumes of heavily polluted
water followed by the removal of excess halogens for taste and odor control
(Acra et al. 1990).
Photocatalysis
The most commonly studied indirect photolysis reaction for water
and wastewater treatment is photocatalysis using titanium dioxide, Ti0 2 ,
as a catalyst. Laboratory, pilot and field studies have demonstrated Ti0 2
catalyzed photodegradation of a wide range of organic chemicals (Table 2-1)
including alcohols, aldehydes, alkanes, alkenes, amines, aromatics,
carboxylic acids, dioxins, dyes, fuel constituents, halogenated
hydrocarbons, herbicides, ketones, mercaptans, pesticides, polychlorinated
biphenyls, solvents, surfactants and thioethers (Aithal et al. 1993; Das et al.
1994; Ellis 1991; Goswami and Jotshi 1992; Legrini et al. 1993; Mills et al.
1993; Ollis 1986; Zhang et al. 1994b). Several researchers have
30
demonstrated the inactivation of microorganisms in water by Ti0 2
photocatalysis (Table 2-2).
Table 2-1. Examples of Photocatalytic Treatment of Water and Wastewater
Investigator (s)
iCONTAMINANT(S)
Catalyst
iLowetal. (1991)
Amines
Ti0 2
Abdullah et al. (1990)
Aniline
Ti0 2
iGoswami et al. (1993) and Oberg (1993)
Benzene, Toluene, Ethylbenzene
jXylene
, Ti0 2
Chlorinated Aromatics
Matthews (1986)
■Chlorinated Benzenes
mo 2
jAhmed and Ollis ( 1984), Hsiao et al.
(1983), Matthews (1986), Nguyen and
:011is (1984), Ollis (1985), Pruden and
iOUis (1983a), and Pruden and Ollis
( 1983b)
jHalogenated Hydrocarbons,
Solvents (THMs, TCE, etc.)
Ti0 2
: \
Haradaetal. (1990)
iOrganophosphorous Insecticides
TiO,/Pt
iAl-Ekabi et al. (1989), Goswami et al.
! 1992 and Li etal. (1992)
phenols & Chlorophenols
Ti0 2
jPehzzettietal. (1988)
iPolychlorinated Dioxins and
iPolychlorinated Biphenyls
Ti0 2 ZnO, CdS,
TiO,/Pt&Fe 2 3 \
Maillard-Dupuy et al. (1994)
Pehzzettietal. (1990)
Pyridine
iS Triazine Herbicides
mo 2
Tio:
Pehzzetti etal. (1989)
Surfactants
TiO : ,
Photosensitization
The body of literature on the use of photosensitization for water
and/or wastewater is much less extensive than that for photocatalysis with
Ti0 2 . Most of the work with regard to microorganisms has been done in the
medical field (Tratnyek et al. 1994). However, some work on virus
inactivation and wastewater treatment was conducted in the early 1970s
(Gerba et al. 1977a; Gerba et al. 1977b; Hobbs et al. 1977; Sargent and
Sanks 1976). Recently, researchers have investigated the use of
immobilized sensitizers for coliform destruction (Savino and Angeli 1985).
31
Table 2-2. Examples of Photocatalytic Treatment of Water and Wastewater
Special
ilNVESTIGATOR(S)
:Blocketal(1997)
Contaminants )
"Escherichia coli, Serratia
■marcescens,
Escherichia coli
Catalyst \ Conditions
fTi0 8 "
Ireland et al. (1993), Wei
let al. ( 1994) and Zhang et
!al. (1994a)
iMatsunaga et al. (1988)
;Matsunaga et al (1985)
Escherichia coli
!Ti0 2
Escherichia coli, Lactobacillus jTib 2 /Pt
acidophilus, Saccharomycces
__;: >
immobilized
bnembrane
!Pt Loaded
jcatalyst
cerevisiae
!Patel(1993)
iBacillus stearothermophilus
^spores, Escherichia coli,
Micrococcus luteus,
iPseudomonas aeruginosa,
Serratia marcescens,
■Staphylococcus aureus
;Ti0 2
[S aitoetal. (1992)
iSjogren and Sierka (1994)
Streptococcus sobrinus
bacteriophage MS2
:TiO, -Addition of Iron
The remainder of the work on wastewater treatment has been
conducted by only a few researchers working in concert. Their
investigations on the treatment of wastewater and sewage effluents using
methylene blue and rose bengal have shown that the technology was viable
in laboratory, pilot and field scale demonstrations (Acher 1984; Acher et al.
1994; Acher et al. 1990; Acher and Juven 1977; Acher and Rosenthal 1977;
Eisenberg et al. 1987a; Eisenberg et al. 1986; Eisenberg et al. 1988). In
addition to the microbiological contaminants, this work addressed
wastewater and the specific industrial contaminant bromacil, indicating
some viability for simultaneous treatment. The use of flavins was
demonstrated for the destruction of herbicides and other organics such as
phenol and aniline (Larson et al. 1989; Larson et al. 1991; Schlauch 1987).
A brief summary of work in this area is shown in Table 2-3.
32
Table 2-3. Summary of Photosensitized Treatment of Water and Wastewater
jlNVESTIGATOR(S)
iCONTAMINANTS
SENSITIZER(S)
Conditions
iAcher and Juven 1977
^Escherichia coli
MB.RB
^oxidation pond
: :
^sewage water
lAcher et al. 1990
ifecal coliform,
MB
pilot plant - sewage j
:enterococci, coliforms,
iefYluents
ipolio viruses
iGerba et al. (1977a) and
icoliform & polio virus
MB
sensitized for 24 h
IGerbaetal. (1977b)
iHobbsetal. 1977
•coliform & polio virus
MB
> :•
iSavino and Angeli 1985
\E. coli
MB, RB, eosin
^Immobilized dyes 1
Burkhard and Guth (1976)
iTriazine Herbicides
Acetone
1
Crosby and Wong (1973)
2,4,5-T
Riboflavin & Acetone
\ I
iHadden et al. (1994), and
ip-cresol, phenol
MB, rhodamine 6G,
high pH (9-10)
iSargent and Sanks (1976)
neutral red, RB
I 1
malachite green,
:
\
hematoporphyrin-D,
\ I
L-hydrochloride,
;i >
:
:
1
acridine orange &
i i
[
others
\ \
ILarson et al. 1989
aniline & phenols
Riboflavin (RF)
\ l
;Triazine Herbicides
iAcher and Rosenthal 1977
ifecal coliform, COD,
MB, RB
berated sewage
MBAS
MB & RB(Algae,
leffluents
iAcher 1984
iOrganics, E. coli,
wastewater
^bacteriophages, polio
bacteria & viruses)
1
ivirus & algae
;
jAcheretal. (1994)
isecondary effluent
coliform & bromacil i
MB
[wastewater
secondary sewage
bffluent
Summary
In terms of effectiveness, the photochemical processes are preferable
for overall water treatment to both the physical processes and straight solar
disinfection, with the exception of desalination, with which it is not
comparable. These processes are effective on both microbiological
contaminants as well as on a wide range of chemical contaminants.
However, in order for these methods to be commercially viable on a large
scale, additional research must be conducted. There are three primary
33
areas where efforts should be concentrated: separation of the
photochemical from the water, including immobilization, elucidation of
harmful intermediates in lieu of complete mineralization and development
of cost efficient or optimal operating parameters. For disinfection the
photochemical processes compare favorably to solar disinfection,
pasteurization, SODIS and halosol. Any of these process can be viewed as
appropriate, particularly for household or small community applications.
In locations where sunshine is in large supply and technically trained
personnel and fossil fuels are in shorter supply, the use of solar based
processes for treatment of water may prove to be a satisfactory alternative.
CHAPTER 3
EXPERIMENTAL DESIGN AND METHODS
Choice of Experimental Parameters
The performance of a photochemical reactor system is affected by a
myriad of variables, only a few of which can be controlled. While the choice
of photoreactant and the availability of light of the appropriate wavelength
range are the two most critical variables, there are other, more subtle
changes in reaction conditions that enhance or degrade the reaction
efficiency. Both the concentration and the physical form of the catalyst or
sensitizer have a marked influence on the efficacy of a given reactor
(Matthews 1991; Wyness et al. 1994). Beyond those factors already
mentioned, pH, the presence or absence of dissolved oxygen, reactor
design, and the nature of the contaminants exhibit the most significant
effect on process reaction rates (Acher et al. 1994; Bedford et al. 1993;
Hadden et al. 1994; Kawaguchi and Furuya 1990).
Development of the experimental design was predicated on analysis
of reported work and preliminary experiments in consideration of the
aforementioned variables. The choices made for the research reported
herein regarding each parameter were noted at the end of the applicable
section.
34
35
Contaminants
Some unique problems identified with groundwater throughout the
United States Virgin Islands (USVI) served as a basis for the selection of
contaminants for this study. Used as source for drinking water, much of
the USVI groundwater is chemically contaminated with light
hydrocarbons from leaking fuel tanks. 1 In addition, due to leakage from
underground sewerage, the microbiological contamination is rather
extensive. 2 A 1986 study of USVI waters found microbiological
contamination in the form of Streptococcus, Klebsiella, Acinetobacter spp.,
Enterobacter, Pseudomonas, Salmonella and Escherichia coli (Canoy and
Knudsen 1986).
To simulate contamination from leaking fuel tanks, benzene, toluene
and xylene were used as chemical contaminants. E. coli, Serratia
marcescens and Pseudomonas aeruginosa were used as microbiological
contaminants, indicative of the contamination identified by Canoy and
Knudsen (1986), and what might be present from leaking sewerage.
Catalyst Choice
A number of semiconducting materials have been tested for use as
photocatalysts in water and wastewater treatment. In order for a material
to be effective for solar photocatalytic water treatment, it must be
photoactive, able to use visible and/or near UV light, biologically and
chemically inert, stable under irradiation, inexpensive, and non-toxic to
humans and aquatic organisms (Carey and Oliver 1980; Mills et al. 1993).
1 From private conversation with Bruce Green of Carribean Infratech.
2 Ibid.
36
Several researchers have tested semiconductors for photoactivity,
including barium titanate, BaTiO,, cadmium sulfide, CdS, tungsten oxide,
W0 3 , titanium dioxide, Ti0 2 , zinc oxide, ZnO, and zinc sulfide, ZnS (Blake
1994). On the whole, Ti0 2 is more active than the others (Blake 1994).
Barbeni et al. (1985) evaluated four other semiconductor oxides relative to
Ti0 2 for the photocatalytic degradation of pentachlorophenol and found
photocatalysis to be the most efficient. In studies of the destruction of
dichlorobenzene using ZnO, W0 3 , platinized Ti0 2 and untreated Ti0 2 , the
Ti0 2 photocatalyzed samples reacted faster (Pelizzetti et al. 1988).
Carey and Oliver (1980) evaluated several semiconductor oxides for
stability under irradiation in neutral aqueous solution (Table 3-1). Of the
semiconductors tested, only those containing titanium were found to be
photostable. With an optical band gap of 2.4 eV, CdS is highly photoactive
and excited by visible light, appearing to be attractive as a photocatalyst.
However, as is typical for semiconductors which absorb visible light, it is
not photostable and tends toward photoanodic corrosion (Davis and Huang
1991; Mills et al. 1993). In the case of cadmium sulfide this leads to the
precipitation of undesirable and ultimately toxic compounds, as shown in
equation 3-1.
CdS + 2h + -> Cd 2+ + Si ( 3-1 )
Considering all of the evidence Ti0 2 seems to be the most desirable for
photocatalytic processes to date. Ti0 2 in anatase form is the most
37
commonly used, due to its chemical stability, ready availability and
photoactivity (Blake 1994; Zhang et al. 1994b).
Table 3-1. Photostability of Semiconductor Oxides Tested by Carey and
Oliver (1980)
Semiconductor
BaTiOs
CaTi0 3
MgTi0 3
SrTi0 3
Ti0 2 (anatase)
Ti0 2 (rutile)
V 2 5
ZnO
ZnTiO,
Photostable
yes
yes
yes
yes
yes
yes
no
no
yes
•:o:-:->:-:-r-:->>>>>:-:->>-:-:->>>:-:-:-:-:-x->xoc->x-:-xo:v-:-:->:->>:->>>:
-:-:-:-:-:-:-:-:-:-:-:-:-:-:-:-:-r-r-»>r:-:->:-»x-»x-
There have been a number of efforts to increase the efficiency of Ti0 2
by surface modification of the catalyst or substitution doping. Loading of
the Ti0 2 surface with noble metals has been used to enhance electron
transfer (production of hydroxyl radicals) and to prolong the life of the
oxidation site at the exterior surface (Blake 1994; Zhang et al. 1994b).
Silver-loading of anatase Ti0 2 increases the efficiency for the destruction of
chloroform and urea by 10% and 67%, respectively (Kondo and Jardim
1991). Other metals used for surface modification are Pt, Rh, Cu, Ni and
Pd. While these metals have been shown to increase efficiency, the cost and
complexity of the surface deposition process are prohibitive for use in most
communities. Substitution doping of Ti0 2 presents the same difficulty. For
these reasons anatase Ti0 2 , Degussa P25, was used for this research.
Choice of Photosensitizer
In addition to the chemical criteria outlined previously for
photosensitizers, they must also be inexpensive and non-toxic. Methylene
38
blue is the photosensitizer commonly used in water treatment research. It
is preferred because it is inexpensive, absorbs preferentially at 670 nm, a
wavelength which easily penetrates wastewater effluent, and has a very
low toxicity. Methylene blue is administered orally in humans for
medicinal purposes (Gerba et al. 1977b; Hobbs et al. 1977).
Martin and Perez-Cruet (1987) evaluated a number of dyes for
suitability as sensitizers. Using sterile sea water with a salinity of 28 ppt,
twelve dyes were studied for absorption tendency by clams (Mercenaria
mercenaria) and photodynamic action against Escherichia coli. Of the
dozen dyes tested, five were considered suitable for further testing by
Martin and Perez-Cruet, and rose bengal showed the most promise. Table
3-2 shows the order of effectiveness of selected dyes against E. coli as
determined by Martin and Perez-Cruet (1987).
Other researchers have found methylene blue to be the preferred dye
sensitizer, although rose bengal seems to work almost as well under most
circumstances (Acher and Rosenthal 1977; Gerba et al. 1977b; Sargent and
Sanks 1976; Savino and Angeli 1985). Several researchers (Larson et al.
1989; Mopper and Zika 1987; Schlauch 1987) have investigated the use of
flavin sensitizers. Their research suggests that riboflavin and lumichrome
are both good photosensitizers.
Acetone is the one other photosensitizer which seems to have given
good results for water treatment. In tests for the photodecomposition of the
herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), both acetone and
riboflavin showed promise (Crosby and Wong 1973). Burkhard and Guth
39
(1976) also found acetone effective for the photodegradation of triazine
herbicides. However, acetone is known to cause systemic effects when
ingested by humans (Sax and Lewis 1989).
Based on this information it appears that the research of
photosensitizers is less conclusive than that for photocatalysts, warranting
further testing. Therefore, both methylene blue and rose bengal were
selected for further evaluation.
Reactor Desig n
The overwhelming majority of the research on reactor design for
photochemical water treatment has been conducted for semiconductor
photocatalysis, primarily with Ti0 2 (Blake 1994). However, since the
reactions follow similar mechanisms, the same principles should apply to
both photocatalysis and photosensitization.
The two major reactor options are reactors using catalyst suspended
in slurry or those in which a fixed supported catalyst is employed (Blake
1994). While the bulk of the research for water and wastewater treatment
has been conducted using slurries of titanium dioxide, there has also been
a great deal of research in the area of immobilizing the catalyst using a
number of different media, with varying results (Blake 1994). Benefits for
the use of supported catalyst are the elimination of the need for separation
and recovery of the catalyst and a possible increase in the reaction rate
(Zhang et al. 1994b).
Researchers at the University of Florida tested both flat plate
photoreactors (Wyness et al. 1994) and shallow pond reactors (Bedford et al.
40
1993) for the destruction of 4-chlorophenol (4-CP) using Ti0 2 adhered to
fiberglass mesh. They found that the same reactor systems performed
better with the slurry catalyst than with the fiberglass mesh. For the flat
plate configuration, reaction rates were two to five times faster (Wyness et
al. 1994).
Table 3-2. Order of Effectiveness of Dyes at 10" 4 M Concentration onE. Coli
After 24 Hours Exposure to Light at Room Temperature
Light Intensity
i7 -2 -1
utm sec
E. coli colony coverage in quadrant areas 3 , mean ± SD
Dye
1
2
3
4
Control
75 b
8.7±0.5
8.011.1
4.512.0
0.8 1 0.4
Control
300 c
9.010.5
9.010.5
6.6 1 0.9
1.210.4
Rose Bengal
75
300
Erythrosine
75
7.011.4
300
Eosin Yellowish
75
6.012.8
0.510.7
300
1.010.5
Zinc Phthalocyanine-
75
7.011.4
4.014.2
tetrasulfonate
300
Acridine Orange
75
8.0 1 0.5
1.510.7
0.510.7
300
5.513.5
0.5 1 0.7
Methylene Blue
75
9.010.5
4.510.7
1.010.5
300
Fluorescein Sodium
75
9.010.5
7.510.7
3.510.7
0.310.1
Salt
300
8.510.7
2.012.8
Alphazurine A
75
9.010.5
7.512.1
1.510.7
300
9.010.5
8.510.7
4.512.1
0.510.7
Rosolic Acid
75
9.010.5
6.012.8
2.011.4
300
Alcian Blue
75
9.010.5
7.510.7
2.011.4
0.510.7
300
Hematoporphyrin
75
9.010.5
8.510.7
4.513.5
1.612.1
300
9.010.5
8.510.7
4.510.7
0.810.4
Alizarine S
75
9.010.5
9.010.5
4.512.1
0.8 1 0.4
Monohydrate
300
9.0 + 0.5
9.010.5
5.011.4
1.010.5
Streaked areas: 1, first streak; 2, streaks from first
streak; 4, streaks from third streaks. Temperature,
Martin and Perez-Cruet (1987).
streaks; 3, streaks from second
25°C. c Temperature, 28°C. Source:
41
Zhang et al. (1994) compared the performance of a number of
different optimized catalyst support options with Ti0 2 slurry using a flat
plate reactor configuration. Of those supports tested, all except glass beads
performed as well as, or slightly better than, the slurry, with silica gel
performing best.
Hofstadler (1994) evaluated titanium dioxide-coated fused-silica glass
fibers for the degradation of 4-CP and reported degradation rates 1.6 times
higher than with Ti0 2 slurry. Some other silica based supports which have
been evaluated were coated sand (Matthews 1991) and glass (Lu et al. 1993).
Matthews found that suspensions of Ti0 2 coated sands were much easier to
deal with in terms of separation, but were mass transfer limited. The
work by Lu et al., using Ti0 2 supported on the inner surface of a glass tube
reactor, indicated the possibility of catalyst reuse.
Fox et al. (1994) examined the effect of zeolite supported Ti0 2 and
Ti0 2 pillared clays on the degradation of alcohols and found a slight
decrease in photoactivity relative to Ti0 2 slurry. Matsunaga et al. (1988)
found Ti0 2 supported on an acetylcellulose membrane to be effective for the
destruction of Escherichia coli. Other supports tested for Ti0 2 were
activated carbon (Uchida et al. 1993), ceramic membranes (Aguado et al.
1994), wood chips (Berry and Mueller 1994), metal, polymer, and thin films
(Blake 1994).
Some research has also been conducted on the immobilization of
photosensitizers. Savino and Angeli (1985) examined the effectiveness of
methylene blue, rose bengal, and eosin on polystyrene beads, and
42
methylene blue on granular activated carbon, silica gel, and XAD-2
(polystyrene resin). They found that all of the immobilized dyes were
effective for the destruction of Escherichia coli, but methylene blue on
activated carbon was the most effective.
Keeping the initial criteria in mind, ease of use and low operational
and capital cost, a number of reactor designs were quickly ruled out. The
methods for immobilizing catalyst all require fairly extensive preparation,
including precipitation and calcination, in almost all cases. Therefore, the
current research was conducted using suspended Ti0 2 and dissolved
sensitizers. The question of the feasibility of immobilized catalyst and/or
sensitizer was left for another study.
There are a number of options available for the specific design of a
reactor using slurry catalyst. In computer simulations of the destruction of
TCE in batch flat plate and parabolic reactors, flat plate reactors yielded a
larger treatment volume than did the concentrating and one-axis tracking
parabolic reactors (Saltiel et al. 1992). Wyness et al. (1994) found that flat
plate reactors were effective for chemical photodegradation with
suspensions of titanium dioxide. Bedford et al. (1993) found that the
shallow pond configuration was effective for the destruction of 4-CP. This
minimalist configuration is attractive because of its potential for low capital
and maintenance costs.
For photosensitization the reactors have more closely resembled
chemical reactors. Plug-flow reactors were successfully tested for the
treatment of secondary effluent (Eisenberg et al. 1988), and continuous flow
reactors showed promise in the sensitized photodegradation of
43
chlorophenols (Li et al. 1992). Acher et al. (1990; 1994) successfully used a
series of tank reactors which were similar to the shallow pond
configuration evaluated by Bedford et al. (1993). The laboratory reactors for
this study were designed to mimic the shallow pond configuration.
EH
Ti0 2 is significantly affected by the pH of the aqueous solution in
which it is suspended. Particle size and charge and the position of the
valence and conduction bands are all a function of the pH of the solution
(Mills et al. 1993). Block et al. (1997) found a neutral to acidic pH range best
for the Ti0 2 photocatalyzed inactivation of bacteria.
A number of researchers have investigated the effects of pH on the
photocatalytic degradation rate of organics in aqueous suspensions
(Bahnemann et al. 1991; Glaze et al. 1993b; Kawaguchi and Furuya 1990;
Matthews 1986; Tseng and Huang 1990; Tseng and Huang 1991; Vidal et
al. 1994). Kawaguchi and Furuya (1990) reported an increase in
photocatalytic effect in acidic solution. The general consensus is that pH
has little (no more than one order of magnitude) effect on the reaction rate,
but that neutral pH provides the most efficient degradation. Other apparent
pH effects are attributed to anionic effects from chemicals used for pH
control. While pH was not a major factor in the photocatalytic reactions, it
was necessary to seek an optimum pH for the simultaneous treatment of
chemical and microbiological contaminants. In the research reported
herein, photocatalytic experiments were conducted at neutral and acidic
pH.
44
Photo sensitization is much more pH dependent. In studies of
methylene blue photodisinfection processes, pH values ranging from 8.6 to
10 were found to be optimum (Acher et al. 1994; Acher et al. 1990; Gerba et
al. 1977b; Melnick et al. 1976). The same pH dependence was seen with
methylene blue and rose bengal for the photodegradation of organic
chemicals (Hadden et al. 1994; Li et al. 1992). In photosensitization of
bromacil using methylene blue and rose bengal, reaction rates increased as
pH values increased, with the highest rates at pH 9-10 (Eisenberg et al.
1986; Eisenberg et al. 1988). Based on this information, the sensitizer
experiments for this research were conducted in neutral and basic
environments.
Catalvst/Sensitizer Concentration
The concentration of the photocatalyst and photosensitizer needed to
be optimized in order to obtain meaningful comparison data. An optimum
of 0.1% Ti0 2 concentration was found to be effective for BTEX by Goswami et
al. (1993) and Oberg (1993). Patel (1993) and Block et al. (1997) found that
0.01% Ti0 2 concentration worked best for the photocatalytic destruction of
bacteria. Therefore a range of Ti0 2 concentrations, from 0.01% to 0.1%
were tested in the laboratory in order to optimize the concentration for
simultaneous photocatalysis.
In pilot plant studies Eisenberg et al. (1988) found that concentration
of methylene blue ranging from 1 to 10 mg/1 were sufficient for the
photooxidation of bromacil. Acher and Juven (1977) conducted
photosensitization experiments with sewage effluent and reported an
increase in the destruction of coliforms with a corresponding increase in
45
methylene blue concentration, up to 5.0 mg/1. However, in pilot plant
studies, smaller concentrations (less than 1.0 mg/1) were effective (Acher
et al. 1994) and concentrations higher than 0.9 mg/1 methylene blue
hindered light penetration (Acher and Rosenthal, 1977). The
photosensitization screening experiments for this research were conducted
at several levels of concentration, ranging from 0.01 mg/1 to 10 mg/1.
Laboratory Experimental Desig n
In this research full factorial designs were used for both the
photocatalytic and photosensitization experiments. While the designs
differed slightly the parameters tested were the same, catalyst/sensitizer
concentration, pH, and light. A two dimensional control was imbedded in
the experimental design by way of the dark experiments and the level with
no photochemical. For the photocatalytic experiment four levels of catalyst
concentration, two levels of pH, two levels of light, and redundant reactors
were used, as shown in Table 3-3. For each of the two dye sensitizers tested,
methylene blue and rose bengal, five levels of sensitizer concentration, two
levels of pH, and two levels of light were used, as shown in Table 3-4. The
photocatalytic experiments were repeated twice and the photosensitization
experiments were repeated three times.
In the combination experiments no pH adjustments were made. The
experiments were conducted with 5 mg/L methylene blue and 0.01% Ti0 2 .
Controls for this experiments were no photochemicals, Ti0 2 only and
methylene blue only. The full design, repeated three times, is shown in
Table 3-5.
46
Table 3-3. Design for Ti0 2 Photocatalytic Lab Experiments
Contaminants
Treatment One Treatment Two
If EX and Bacteria If EX and Bacteria
Light
None
None
pH
Neutral, 7 (±0.5)
Acid, 4 (±0.5)
Ti0 2 Concentration
None 0.01% 0.05% : 0.10%
None 0.01% 0.05% 0.10%
Contaminants
BTEX and Bacteria
BTEX and Bacteria
Light
UV Lamps @ 29 W/m 2
UV Lamps @ 29 W/m 2
pH
Ti6 2 Concentration
Neutral, 7 (±0.5)
None 0.01% 0.05% 0.10%
Acid, 4 (±0.5)
None 0.01% I 0.05% 0.10%
Table 3-4. Design for Photosensitization Lab Experiments
Treatment One
If EX and Bacteria
None
Treatment Two
If EX and Bacteria
None
Contaminants
Light
•; -
pH
Dye Cone, mg/L
Contaminants
>:•"-'•■-•-*-:-:•:---:-:->:-----:----•:-:-'-:-:--::-•-:-:•:-!-*-:•--------:-:.:.:-:■:-:>-:.:-:.:.;
Basic, 10 (±0.5) Basic, 10 (±0.5)
None [ 0.10 15 10 None 0.10 1 5
M'X*x-:-:-x-:-:-:-:-:-:-:-:-:-x-x-:-:*:-:->^
BTEX and Bacteria BTEX and Bacteria
! 10
.:.x-x-x-x-x-x-x-x-:..xx-x<-"-x:-v-x-x-x*x-x-x>
Light Sunlight
pH Basic, 10 (±0.5)
Sunlight
Baric, 10 (±0.5)
Dye Cone, mg/L
:w:-:-:-:-:-:-:->:-;-;-;-;-:-:-x-:-:-:-:-:-:-:-:
1 None \ 0.10 j 1 | 5 j 10 j None j 0.10 | 1
:«»»»>>™ww:v:v:w:'^^^^^^^
10
Table 3-5. Design for Combination Lab Experiments
Contaminants
Treatment One
Iflx and Bacteria
>:-:-X-X-:o:-:-:-v.:-:-:-:-y.:.:.;.v.:.:
Treatment Two
BTEX and Bacteria
:•:•:■:■:■:■>:•:-:-: -»:-:-:-:-:-:-x-x-x-»:-:-:
nmi Li gh t None None
Photochemical j _Nope J0.O1% f iO^ 5 mg/L ."MB""" Both None:0j01%f iCv5 mg/L MBJIoSi
Materials and Methods
Reaction Vessels
The photocatalysis reaction vessels were covered Pyrex dishes
(Figure 3-1), which allowed light transmission above wavelengths of X > 300
47
nm, the shortest wavelength that reaches the earth's surface from the sun
(Hsieh 1986). This filtered out the germicidal effects of the ultraviolet light
which would not be present in naturally occurring sunlight.
Water line
60
in in
Lid removed to take
samples
100 mm
Figure 3-1. Ti0 2 Reaction Vessel
In order to eliminate problems of air stripping and ensure that the
reactor was airtight, a slightly modified version of the photocatalytic
reaction vessel was used for both photosensitization and the combination
experiments. The reactor was equipped with a glass blown sampling port
plugged with a butyl rubber septum and sealed with parafilm (Figure 3-2).
The reactors were filled to the rim of the vessel in order to minimize head
space.
Bacterial Inoculation
Cultures were prepared using trypticase soy broth nutrient, and
incubated for 24 hours at 35°C. Three serial dilutions of 1:100 were
48
prepared using distilled deionized water. Photocatalytic reactors were
inoculated with 400 \il ofE. coli, 400 \i\ of Serratia marcescens and 200 ul of
Pseudomonas aeruginosa, using the 2nd dilution of each culture.
Water line
Parafilm to
seal
60
£
mm
Sample port
with septum
100 mm
Figure 3-2. Photosensitization Reaction Vessel
Only E. coli was used for photosensitization experiments, and the
reactors were inoculated with 45 [i\ of the first dilution of the culture. In all
cases the third dilution was used to confirm that the cultures were viable.
This procedure is shown graphically in Figure 3-3.
E.coli
Slant
£. coli culture
in Trypticasc
Soy Brot h
Initial Count
Agar Plate
(Incu bated)
photosensitization \
phoUKatalysis
Experimental
Glass Reactor
Figure 3-3. Graphical Representation of Bacterial Inoculation
49
Initial bacterial densities in the reactors ranged from 10 3 to 10 4
colonies per ml, with most values falling around 3.5 x 10 3 colonies per ml.
Bacteria were obtained from American Type Culture Collection (ATCC).
Reactor Chamber
The reactor chamber was used for all of the photocatalytic
experiments and the dark experiments for photosensitization. The
chamber was a metal box equipped with 32 ultraviolet low-pressure
mercury lamps and painted in flat black (Figure 3-4). The lamps were
purchased from Southern New England Ultraviolet, model RPR-3500. The
design output of the lamps was 3500A. Reactors were placed approximately
35 cm from the light source, at which point the ultraviolet irradiation
measured was 29 W/m 2 . External light was blocked via a hinged metal
door which fit snugly over the chamber. The lamps were turned off for the
dark experiments.
Photocatalvsis Reactor Setup
The reactors were loaded with deionized distilled and pH adjusted
water and a combination of bacteriological and volatile organic chemical
(VOC) contaminants, for a total volume of 100 ml. The chemical
contaminants were approximately 1 ppm each of benzene, toluene and
mixed xylenes, referred to as BTEX, and the bacterial species were
Escherichia coli, Pseudomonas aeruginosa and Serratia marcescens.
Redundant reactors were placed for two to four hours in a reactor chamber
either with or without light.
50
Figure 3-4. Ultraviolet Light and Dark Reactor Chamber
As shown in Table 3-3, four Ti0 2 concentrations were used for the
experiments: 0.1%, 0.05%, 0.01% and none. The catalyst used was Degussa
P-25. The water was adjusted to an acid pH (4.0 ± 0.5) and a neutral pH (7.0
± 0.5) with hydrochloric acid and sodium hydroxide. After pH adjustment
the water was autoclaved to remove any microbiological contamination.
The 100 ml reactors were illuminated for 2 to 4 hours in the reactor
chamber.
Photocatalvsis Sampling and Analysis
Samples for chemical analysis were taken prior to irradiation, after 5
minutes, 15 minutes, 30 minutes and one hour of irradiation and at the
same time intervals in the dark chamber. Samples were taken with a
sterile syringe and placed directly into amber borosilicate screw cap vials
with Teflon™ septa, and refrigerated until analysis. The samples were
analyzed by a modification of the EPA purge and trap method using an SR
51
8610 gas chromatograph with PID detector (Abeel et al. 1994; Bellar and
Lichtenber 1974; Oberg 1993). The method used was sensitive to a low
concentration of about 1 ppb for the components in question.
For evaluation of disinfection efficacy, duplicate petri dishes
containing plate count agar nutrient were inoculated with 100 fil from each
reactor. Two replicates were taken at 0, 30, 60, 120 and 240 minutes,
yielding four counts for each set of conditions per experiment. The
inoculated plates were spread and incubated for 24 hours at 35°C. After 24
hours the number of bacterial colonies on each plate were counted.
Photosensitization Reactor Setup
The reactors were loaded with deionized, distilled, pH adjusted water
and a combination of bacteriological and volatile organic chemical (VOC)
contaminants to the top of the container, a total volume of approximately
450 ml. The chemical contaminants were approximately 1 ppm benzene
and 1 ppm toluene, referred to as BTEX, and the bacterial species was
Escherichia coli, as noted above. The reactors were placed either in
sunlight or in a closed, dark reactor chamber (Figure 3-4) for four hours
and constantly agitated with a magnetic stirrer.
As outlined in Table 3-4, five sensitizer concentrations of either
methylene blue or rose bengal, were used for the experiments: 0.1 mg/1, 1.0
mg/1, 5 mg/1, 10 mg/1 and none. Both the methylene blue and the rose
bengal were purchased from Fisher Scientific. The water was adjusted to a
neutral pH (7.0 ± 0.5) and a basic pH (10.0 ± 0.5) using sodium hydroxide.
After pH adjustment the water was autoclaved to remove any
microbiological contamination.
52
Photosensitization Sampling and Analysis
A sterilized 10 ml syringe was used for taking samples via the
sample port. Samples were taken at 0, 5, 15, 30, 60, 120 and 240 minutes by
sterilized syringe and transferred into amber borosilicate screw cap vials
with Teflon™ septa, and refrigerated in a standard commercial
refrigeration unit until they were analyzed.
For evaluation of disinfection efficacy, petri dishes containing plate
count agar nutrient were inoculated, in triplicate, with 100 |il from each
sample. Three replicates were taken per sample. The inoculated plates
were spread and incubated for 24 hours at 35°C. After 24 hours the number
of bacterial colonies on each plate were counted. Chemical analysis was
the same as that used for Ti0 2 photocatalysis.
Combination Experimental Setup. Sampling and Analysis
The setup, sampling, and analyses for the combination experiments
were very similar to that of the photosensitization experiments. The
reactors were loaded with deionized, distilled water and a combination of
bacteriological and volatile organic chemical (VOC) contaminants to the top
of the container, a total volume of approximately 450 ml. The chemical
contaminants were approximately 1 ppm benzene and 1 ppm toluene,
referred to as BTEX, and the bacterial species was Escherichia coli, as
noted above. The reactors were placed either in sunlight or in a closed,
dark reactor chamber (Figure 3-4) for one hour and constantly agitated with
a magnetic stirrer.
As outlined in Table 3-5, four photochemical concentrations of
methylene blue and/or Ti0 2 were used for the experiments: no
53
photochemical, 0.01% Ti0 2 , 5 mg/1 methylene blue, and 0.01% Ti0 2 and 5
mg/1 methylene blue.
A sterilized 10 ml syringe was used for taking samples via the
sample port. Samples were taken at 0, 5, 15, 30, 60, 120 into amber glass
screw cap vials with Teflon™ septa. The samples were refrigerated in a
standard commercial refrigeration unit until they were analyzed.
For evaluation of disinfection efficacy, petri dishes containing plate
count agar nutrient were inoculated with 100 ul from each sample. Three
replicates were taken per sample. The inoculated plates were spread and
incubated for 24 hours at 35°C. After 24 hours the number of bacterial
colonies on each plate were counted. Chemical analysis was the same as
that used for Ti0 2 photocatalysis.
Experim ents for Confirmation of Previous Work with Bromacil
One set of experiments was conducted to confirm the previous work
with photosensitizers in which methylene blue was used for the destruction
of bromacil in wastewater. Duplicate photosensitization reaction vessels
(Figure 3-2) were loaded with approximately 1300 ppb bromacil, 5 mg/L
methylene blue and deionized water. After irradiation in sunlight for four
hours, the reactor contents were analyzed by GCMS. The bromacil used for
the experiments was tech grade obtained from E. I. DuPont de Nemours
and Company, Inc.
CHAPTER 4
RESULTS AND DISCUSSION
The results of laboratory experiments are presented and discussed in
this chapter. The results are divided by experiment type: dye
photosensitization, Ti0 2 photocatalysis and combination experiments. A
general discussion is presented at the end of the chapter. Raw data for all
experiments are contained in Appendix A.
Dye Photosensitization
Laboratory experiments were conducted to determine the effects of
dye concentration and pH on the destruction rate of Escherichia coli and
aromatic hydrocarbons (benzene and toluene) in sunlight. As described in
Chapter 3, the experiments were conducted with the following treatments :
• methylene blue (MB) and rose bengal (RB),
• sunlight and dark,
• pH 10 and pH 7,
• 0,0.1, 1,5 and 10 mg/L of dye.
In order to ensure reproducibility of the results, each set of
experiments was conducted three times. A complete set of experiments
was represented by one reactor for each of the sets of conditions highlighted
above, for a total of 40 reactors per set. Five reactors were run at a time,
each reactor containing a different concentration of a single dye (either
methylene blue or rose bengal) with all other parameters the same.
54
55
Samples were taken from each reactor at 0, 5, 15, 30, 60, 120 and 240
minutes and refrigerated immediately. Three replicates were plated from
each sample for microbiological analysis. The remainder of the 0, 60 and
240 minute samples was refrigerated and saved for chemical analysis.
For the experiments conducted in sunlight, the light was measured
and recorded over the duration of the experiment, and ranged from 542
W/m 2 to 892 W/m 2 . The average total insolation (incident solar radi ation)
measured in each experiment is given in Table 4-1 and graphs of the total
insolation are shown in Appendix B.
Table 4-1. Insolation Measurements from Dye Sensitization Experiments
Set Conditions Insolation, W/m 2
#1 ' Methylene Blue, pH 7 685
Methylene Blue, pH 10 671
Rose Bengal, pH 7 746
Rose Bengal, pH 10 715
#2 Methylene Blue, pH 7 665
Methylene Blue, pH 10 542
Rose Bengal, pH 7 856
Rose Bengal, pH 10 775
#3 Methylene Blue, pH 7 892
Methylene Blue, pH 10 696
Rose Bengal, pH 7 841
Rose Bengal, pH 10 749
Experimental sets were conducted on different days, and though
efforts were made to minimize the differences between sets, both solar
insolation and initial contaminant concentrations did vary from one set to
another. The mean, standard deviation, and range of these parameters for
all experiments are shown in Table 4-2.
OD
Table 4-2. Descriptive Statistics of Measured Data for all Experiments
MB Parameter
Mean
StdDev
Min
Max
Sunlight, W/m 2
692
112
542
891
Sunlight, pH 7, W/m 2
743
129
665
891
Sunlight, pH 10, W/m 2
641
50
542
696
Initial Coliform Density, cfu/L x 10 3
784
365
27
1453
Initial Benzene concentration, ppb
676
210
377
1218
Initial Toluene concentration, ppb
314
139
136
770
:*>:v:v:-:-:-:v:v:-:v-:-:-x-:-:-:-:->:-:-:-x^
WflWMCWffWWWflMflWMWWI
RB Parameter
Mean
StdDev
Min
Max
Sunlight, W/m 2
781
56
715
856
Sunlight, pH 7, W/m 2
815
60
746
856
Sunlight, pH 10, W/m 2
746
30
715
775
Initial Coliform Density, cfu/L x 10 3
816
375
187
1680
Initial Benzene concentration, ppb
560
262
296
1407
Initial Toluene concentration, ppb
426
226
155
1026
The data, as well as the impact of each of the measured and
controlled parameters, are explored in more detail below, and results are
compared with the work of Eisenberg et al. 1987b, Acher et al. (1994), and
Acher et al. (1990), for the photosensitized disinfection and bromacil
destruction in secondary treated wastewater effluent.
General Comments About Experimental Data
The average standard deviation of the disinfection data was 25% for
methylene blue experiments and 13% for rose bengal experiments (Table 4-
3). Plates on which the colonies were not individually identifiable and those
with severe contamination were not counted, which resulted in the loss of
approximately 20% of the 840 plates in a given experimental set. Due to
contamination of the incubator, all 105 of the plates from the sunlight, pH
10, methylene blue experiment in set number two had to be discarded. In a
few instances the samples were dropped and broken before they could be
plated.
57
The initial (t=0) disinfection samples for the dark, pH 10, rose bengal
experiment in set number one were abnormally, though consistently, low.
The low values were attributed to not allowing time for adequate mixing in
the reactors prior to drawing the first sample. Since the values were
consistent from one reactor to the next, the data could not be treated as
outliers, but accommodations were required for accurate interpretation.
For this set of data, the fractional survival values were calculated using the
5 minute instead of the zero minute samples.
The average standard deviations of the detoxification data were 10%,
or less, of the average values as shown in Table 4-3. Sample loss for
detoxification occurred when the sample was dropped and broken prior to
analysis, which occurred twice in experimental set number three. The
samples on either side of the dropped sample, 8^, were analyzed, and the
sample value for the desired time was interpolated. When the dropped
sample was an initial sample, 33 , the 5 minute sample was substituted.
Chemical samples were generally analyzed within two weeks of the
experiment.
Table 4-3. Average Standard Deviations for all Dye Photosensitization
Experiments
•^^^^^^^^^^^.■^.■.■.■.■.■.■.■^.■.■.■.■.•.•.■.■.■.•.■.■.■.■.■^rr^^>^>>^^-^^.
Benzene (ppb) Toluene (ppb) E.Coli
StdDev "Avg SWDev Avg ' ~%rfUytal
Methylene Blue 51 578 29 375 —
Rose Bengal 46 487 36 363 13
.-.■.■.■.-.-.•.-.•.-.•.•:•:•;-:-:■:-:•:-.-.-.-.
^^^r^^rrrrrrrr^.^^^>^^^.^^^------^^^^^r^^^^^-
58
Statistical Treatment of the Data
Microsoft Excel version 5.0 for the Macintosh was used for statistical
analysis of the data. For the more common calculations, including least
squares linear regression, the functions available in the software package
were used. All other values were calculated using the equations as noted
throughout this section.
Since the sample sizes were generally small (less than 30), the entire
populations were used to calculate standard deviation from Equation 4-1.
.o.J "£-'HZ->)
(4-1)
n
For disinfection data analysis, the fractional survival and percent
destruction of colony forming units (cfu) were used for reporting and
analyzing the data. The values used for disinfection data analysis were
obtained by taking the average of the plates for each sample collected within
an experimental set, calculating fractional survival (or % destruction) and
averaging those values across experiments for use. The data, obtained in
this way for methylene blue at 30 minutes, are shown in Table 4-4.
In situations where calculations resulted in a negative percent
destruction, the percent destruction was set to zero. In some instances the
fractional survival exceeded 2.0, specifically, the data from the dark, pH 10,
rose bengal experiment in set one. For that data set, the fractional survival
was calculated relative to the 5 minute samples, i.e. fractional survival =
N t /N 5 .
59
Table 4-4. Mean Fractional Survival (± 31%) of E. coli @ t= 30 minutes in
MB Experiments
:
_t#
Sunlight pH 10 Sunlight pH 7
Dark pH 10
DarkpHT]
i Control
1
0.000 0.172
1.113
1.500
;
2
0.534
1.013
0.169
3
0.084 0.082
0.364
0.503 |
[Average
;0.1 mg/L
1
0.042 0.262
0.000 0.013
0.830
0.592
0.724
VA»AV.W.'.*MV.'JV.V.V.wX
1.547
:
2
0.155
0.841
0.088 \
3
0.009 0.000
0.583
0.540
: Average
;1 mg/L
1
0.005 0.056
0.000 0.007
0.672
0.494
0.718
"a779"1
2
0.013
0.538
0.101
3
0.000 0.000
0.000
0.502 |
| Average
0.000 0.007
0.344
0.461 |
[ 5 mg/L
1
0.000 0.002
0.030
0.000
;
2
0.016
0.007
0.000
3
[ Average
0.000 0.006
0.039
0.011
0.158
1 10 mg/L
1
0.000 0.016
0.034 j
2
0.000
0.000
0.018
! Average
3
0.000 0.000
0.004 0.195
" 0.005*1 ololSB j
v.-.-.-.%%-.-.-.\-.-.*.-.'.*.'.'.-.'.-.-.-.'.v.*. - .-.'>.v.-.\%\%v.%-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-;
Detoxification data were treated in a similar manner. The
concentration data, as parts per billion (ppb), for each experimental set
were normalized to the initial concentration (C t /C ). The normalized values
were averaged across experimental sets. Since only one data value existed
per sample for each experimental set, standard deviations were calculated
across sets only. Outliers were identified using the ASTM recommended
criterion for single samples (ASTM 1988) which uses the following test:
T n = |(x-x n )|/s (4-2)
The critical value of T n is a function of the number of observations and is
obtained from a table (ASTM 1988). Using this criterion, one value was
found to be an outlier at a significance level of 10% (5% for toluene) and
60
subsequently discarded. The outlying sample, the 240 minute, 1 mg/L
sample from RB, dark, pH 10 in experimental set number two, was thought
to have been poorly capped, resulting in volatilization of the sample prior to
analysis.
The data were viewed in several ways. An initial observation was
conducted for the detection of trends and to determine if the desired effect
was achieved. These trends were displayed as a function of time for all of
the average values as x-y scatter plots. If trends of the desired effect,
destruction of contaminants with time, were detected, the data were
analyzed further for the impact of specific parameters on the final results
as described below.
Analysis of Means (ANOM) was applied to obtain a statistical
snapshot of the effect of specific parameters on the outcome. In this
method, mean values and statistical deviations were used to clarify the
significance of each parameter. The ANOM is a variation on a process
control chart and allows for the exploratory analysis of several parameters
simultaneously (Mason et al. 1989). A relatively conservative a-level of 0.05
was chosen to minimize the probability of false alarms. A smaller a-level
was not desirable as it might have resulted in missed signals and would be
inappropriate for this type of exploratory analysis (Wheeler 1990).
The Pooled Variance Estimator was used for determination of
Estimated SD (X) as shown below. Decision limits for the ANOM charts
were calculated using the following equations (Wheeler 1990):
61
Estimated SD (X) = V? ( 4-3 )
n? *• * j on / vw Estimated SD (X) , . . .
(Estimated SD ( X )) = r ( 4-4 )
UDL X = X + H (Estimated SD ( X )) ( 4-5 )
LDL X = X - H (Estimated SD ( X )) ( 4-6 )
where:
s = standard deviation of X,
X = average of observations in a subgroup,
sr = average variance of X,
n = number of observations per subgroup,
X = grand average of all observations,
H = ANOM critical value at a selected a, from table (Wheeler 1990),
UDL X = upper decision limit, and
LDL X = lower decision limit.
Averages which were outside of the decision limits were considered to be
statistically significant, and those parameters were determined to be
influential
In some instances the data were graphically represented. For this
analysis, data were simply categorized according to the parameters of
interest, and standard deviation and mean values were calculated using
the Microsoft Excel functions. These values were then charted, either as
scatter plots or bar charts. Where appropriate, least squares linear
62
regression, also using Microsoft Excel, was performed to identify specific
trends and relationships.
Where clear destruction of contaminants was seen, kinetics were
considered. Results were fitted to first order kinetic equations, and
experimental reaction rate constants were obtained for comparison to
published data. This information is presented in the section on kinetic
considerations, which includes kinetic data for all relevant experimental
sets.
Presenta tion of Results and Identification of General Trends
While disinfection in the presence of aromatic hydrocarbons was
achieved with both rose bengal and methylene blue, simultaneous
detoxification was not observed with either dye. Under the conditions
tested, the presence of MB increased the disinfection rate of water
contaminated with E. coli over sunlight alone.
MB photosensitized disinfection at pH 10 (Figure 4-la) appears to be
slightly more effective than MB photosensitized disinfection at pH 7. At pH
10, all MB concentrations resulted in at least a 99.5% coliform reduction
after thirty minutes of irradiation, compared to 96% reduction with
sunlight alone. With 10 mg/L MB, complete coliform destruction was
achieved after only five minutes of irradiation. No coliforms appeared in
any of the samples taken after irradiation began. The intensity of sunlight
in these experiments ranged from 542 to 696 W/m 2 .
Destruction at pH 7 was not quite as dramatic (Figure 4- lb). The
coliform reduction after 30 minutes ranged from 99.5% with 10 mg/L MB to
96% with 0.1 mg/L MB. Comparatively, only a 74% reduction was attained
with sunlight alone. The intensity of sunlight ranged from 665 W/m 2 to
891 W/m 2 . Differences between pH 10 and pH 7 cannot be attributed to
differences in light intensity since, as shown in Tables 4-1 and 4-2, the
intensity was greater in the pH 7 experiments even though less reduction
was achieved. The difference in values for control reactors would lead one
to conclude that any pH effect was a function of the general disinfection
mechanism rather than of the photosensitization process specifically.
(a)
Avg S.D. = 14.5%
15 30 45
Time (minutes)
60
-♦- Control
-B-0.1 mg/L
-A-1 mg/L
-X- 5 mg/L
-X-10 mg/L
100%
(b)
15 30 45
Time (minutes)
60
c
Control
0.1 mg/L
1 mg/L
-X-5 mg/L
-x-
10 mg/L
Figure 4-1. MB Destruction of E. coli in Sunlight; (a) pH =10, 1 = 542-696
W/m 2 (b) pH =7, 1 = 665-891 W/m 2
avg
avg
64
In the presence of at least 1 mg/L MB and sunlight (542 - 696 W/m 2 ),
complete disinfection occurred within 5 to 30 minutes. However, in the
absence of MB with the same intensity sunlight, complete disinfection
required at least 60 minutes (Figure 4-2). Complete disinfection did not
occur at all in the dark, although a 99% coliform reduction was observed
with 10 mg/L MB in the dark. Mean fractional values for the methylene
blue experiments are presented in Table 4-5.
(a)
15 30
Time (minutes)
-t—
45
60
No MB, Sunlight
-No MB, Dark
1 mg/L MB, Sunlight
1mg/L, MB Dark
(b)
Avg S.D. = 28%
15 30 45
Time (minutes)
60
to MB, Sunlight
-O- No MB, Dark
1 mg/L, Sunlight
1 mg/L, Dark
Figure 4-2. Destruction of E. coli in sunlight with 1 mg/L MB- (a) pH =10
I avg = 542-696 W/m 2 and (b) pH 7, 1 = 665-891 W/m 2
avg
65
Table 4-5. Mean Fractional Survival (±25%) of E. coli in MB Experiments
Control Sunlight pH 10 Sunjfcfrt pHT~" Dark pH 10 Dark pH 7
Ng/N 1133 0.811 0J54 0671
N 15 /N 0.707 0.428 0.626 0.493
N 30 /N 0.042 0.262 0.830 0.724
N 60 /N 0.000 0.013 0.681 0.858
N 120 /N 0.000 0.000 0.449 0.063
Nag/No 0.000 0.000 0.365 0.008
6.1 mg/L ^T^T"™"
N 5 /N 6.030 6.651 6,867 6.609
N 15 /N 0.002 0.234 0.766 0.613
N 30 /N 0.005 0.056 0.672 0.718
N 60 /N 0.000 0.016 0.600 0.363
N 120 /N 0.000 0.005 0.299 0.141
N?4 p /N p 0.000 0.000 0.285 0.077
1 mg/L
N5/N 0MXT~" 0JL94 -™-^ggp-~-» - ~~—^
N 15 /N 0.000 0.011 0.581 0.657
N 30 /N 0.000 0.007 0.344 0.461
N 60 /N 0.000 0.006 0.223 0.312
N 120 /N 0.000 0.002 0.040 0.329
n ^/Nq aooo 0.000 0.006 o.osi
5 mg/L
n 5 /No a666™ H£666 ""06® 6T29?
N 15 /N 0.003 0.014 0.118 0.209
N 30 /N 0.000 0.006 0.039 0.158
N 60 /N 0.001 0.002 0.039 0.139
N 120 /N 0.000 0.002 0.000 0.160
N 2 4o/N 0.000 0.000 0.005 0.012
10 mg/L ""
n 5 /n oooo 6.666 aooo 6376
N 15 /N 0.000 0.010 0.002 0.160
N 30 /N 0.000 0.005 0.005 0.082
N 60 /N 0.000 0.002 0.002 0.076
N 120 /N 0.000 0.000 0.000 0.023
N24 p /N 0.000 0.000 0.005 0.052
Rose bengal was less effective for photochemical disinfection than
was MB. The presence of RB had little, if any, positive effect on the
disinfection rate over sunlight alone, although the experiments at pH 7
appeared to exhibit some photochemical disinfection (Figure 4-3a).
In the experiments conducted at pH 10 (Figure 4-3b), RB had no
positive effect on disinfection over sunlight alone. Coliform reduction of
greater than 99.9% was observed by 60 minutes in sunlight alone; however,
in the presence of RB the same coliform reduction was not evident until the
240 minute samples with 0.1 mg/L RB and the 120 minute samples for all
other RB concentrations. Coliform reduction was about the same by 30
minutes regardless of the RB concentration, with a low of 81% for 10 mg/L
RB and a high of 90% with 1 mg/L RB. The control, sunlight alone, had a
coliform reduction of 88%. The differences are not significant, as all values
fall within the average standard deviation of 21%. The average intensity of
sunlight in these experiments ranged from 715 to 775 W/m 2 .
As was evidenced in the experiments with MB, disinfection appeared
to be less effective at the neutral pH value of 7 (Figure 4-3a). The exception
was with the higher concentrations of RB, 5 and 10 mg/L (Figure 4-4),
where coliform reductions by 30 minutes were 96% and 97%, respectively.
In comparison, coliform reduction in sunlight alone (746-856 W/m 2 ) by 30
minutes was 77%, 78% with 0.1 mg/L RB and 89% with 1 mg/L RB. Mean
values for the fractional survival of E. coli in the rose bengal experiments
are shown in Table 4-6.
While some reduction in both benzene and toluene concentration was
observed with both dyes under every set of conditions, there was a
substantial amount of contaminant (130 - 550 ppb) remaining in the water
(Tables 4-7 and 4-8) after four hours. Initial concentrations ranged from
139 - 1400 ppb as shown in Table 4-2. Figures 4-5 to 4-8 show the
concentration of benzene and toluene as a function of time at various dye
concentrations.
67
(a)
15 30 45
Time (minutes)
60
-6— Control
-O-0.1 mg/L
-A-1 mg/L
-X-5 mg/L
-X-10 mg/L
(b)
100%
90%
AVG S.D. = 16.1%
H (
15 30 45
Time (minutes)
60
— o-
Control
— H-
0.1 mg/L
1 mg/L
5 mg/L
10 mg/L
Figure 4-3. RB Destruction of E. coli in Sunlight; (a) pH = 7, 1 = 746-856
W/m 2 (b) pH = 10, L, = 715-775 W/m 2
The experimental values for both benzene and toluene in MB showed
fairly consistent reductions, with normalized concentrations ranging from
0.59 to 0.87 after four hours. Both the greatest and smallest reductions
corresponded to control reactors, sunlight at pH 10 and dark at pH 7,
respectively.
68
(a)
100%
90%
c
o
o
a
Time (minutes)
No RB, Sunlight
-No RB, Dark
-X- 5 mg/L RB, Sunlight
--•—5 mg/L , Dark
15 30 45
Time (minutes)
60
-♦-No RB, Sunlight
O No RB, Dark
-X-10 mg/L RB, Sunlight
G- 10 mg/L RB, Dark
(b)
Figure 4-4. RB Destruction of E. coli at pH =7, I avg = 715-775 W/m 2 ;
(a) 5 mg/L RB and (b) 10 mg/L RB
Examination of the normalized data (Tables 4-9 and 4-10) did not yield
a different conclusion. Neither chemical contaminant exhibited a
substantial difference in behavior between control and non-control reactors
in either MB or RB experiments, as seen from Figures 4-9 to 4-12.
In RB experiments reductions ranging from 15% to 36% for benzene
and 24% to 47% for toluene in sunlight were observed. One reactor, the
dark control reactor at pH 10, exhibited no reduction at all. However, since
the other controls, both in sunlight and in dark, had destruction rates
69
which were in the middle of the range for the non-control reactors, this
cannot be considered an indication that photochemical action took place.
Table 4-6. Mean Fractional Survival (±13%) of E. coli in RB Experiments
Ccmtroi Sunlight pH 10 Sunlight pH 7 Dark pH 10 Dark pH 7
N 5 /N
0.668
0.714
0.961
0.925
N 15 /N
0.315
0.458
1.074
0.729
N 30 /N
0.122
0.226
0.952
0.762
N 60 /N
0.000
0.001
0.795
0.527
N 120 /N
0.000
0.000
0.660
0.512
N 240 /N
0.000
0.003
0.381
0.331
0.1 mg/L
N 5 /N
0.541
0.599
0.846
0.717
N 15 /N
0.381
0.216
1.058
0.545
N 30 /N
0.131
0.221
0.930
0.649
N 60 /N
0.002
0.006
0.797
0.696
N 120 /N
0.005
0.000
0.617
0.552
N 240 /N
0.000
0.000
0.269
0.451
1 mg/L
N 5 /N
0.498
0.624
1.028
0.436
N 15 /N
0.241
0.462
1.007
0.678
N 30 /N
0.102
0.110
1.033
0.530
N 60 /N
0.009
0.001
1.107
0.625
N 12O /N
0.000
0.000
0.838
0.499
N 240 /N
0.000
0.003
0.461
0.292
5 mg/L
N 5 /N
0.707
0.562
0.966
0.681
N 15 /N
0.447
0.371
1.006
0.970
N 30 /N
0.150
0.044
1.015
0.693
N 60 /N
0.006
0.007
0.920
0.650
N 120 /N
0.000
0.000
0.597
0.820
N 240 /N
0.000
0.000
0.334
0.640
10 mg/L
N 5 /N
0.555
0.516
0.989
0.746
N 15 /N
0.451
0.365
0.884
0.551
N 30 /N
0.188
0.029
0.918
0.537
N 60 /N
0.002
0.000
0.888
0.666
N 120 /N
0.000
0.004
0.659
0.490
N 240 /N
0.000
0.000
0.388
0.478
70
Table 4-7. Benzene (±51) and Toluene (±29) Concentrations (ppb) in MB
Experiments
BENZENE
Time (min)
Sunlight pH 10
Sunlight pH 7
Dark pH 10
Dark pH 7
Control
953
609
632
630
60
686
593
565
643
240
522
545
476
545
0.1 mg/L
767
622
597
646
60
578
533
583
533
240
513
482
399
495
1 mg/L
733
642
729
705
60
643
555
521
554
240
544
527
419
500
5 mg/L
707
658
604
662
60
626
502
562
597
240
564
418
385
491
10 mg/L
762
583
596
679
60
567
535
565
548
240
478
456
431
483
TOLUENE
Time (min)
Sunlight pH 10
Sunlight pH 7
"DarrpWlF
„_j^__
Control
499
278
269
310
60
298
250
224
312
240
214
221
176
234
0.1 mg/L
358
282
264
324
60
248
217
245
243
240
210
158
141
211
1 mg/L
326
297
319
357
60
275
235
207
256
240
226
208
157
209
5 mg/L
330
300
261
327
60
261
215
248
281
240
230
160
131
203
10 mg/L
347
266
255
331
60
233
225
227
261
240
183
171
155
211
The greatest apparent reductions seemed to correspond to higher
initial concentrations and exposure to sunlight. This type of behavior
would be consistent with benzene and toluene being trapped in the vapor
space above the water line. Although head space was kept to a minimum,
as the samples were drawn from the reactor, head space increased.
Though temperature was not a consistently measured parameter, an
increase in temperature was observed, probably due to sunlight and friction
71
from the magnetic stirrers. The combination of temperature and head
space increase would necessarily lead to volatilization of the chemical
contaminants in the vapor space. Spot temperature checks with
temperature strips on the outside reactor glass yielded values in excess of
96°F in sunlight.
Table 4-8. Benzene (± 46) and Toluene (± 36) Concentrations (ppb) in RB
Experiments
BENZENE
Time (min)
Sunlight pH 10
Sunlight pH 7
Dark pH 10
DarkpH7
Control
716
746
432
497
eo
692
557
446
466
240
499
539
447
425
0.1 mg/L
542
657
478
504
60
508
541
474
440
240
463
508
371
417
1 mg/L
593
618
463
516
eo
533
513
399
438
240
389
504
332
379
5 mg/L
611
646
437
515
60
516
524
434
413
240
386
476
350
365
10 mg/L
583
635
483
461
60
420
513
438
419
240
375
483
371
341
TOLUENE
Time (min)
Sunlight pH 10
Sunlight pH 7
Dark pH 10
Dark pH 7
Control
543
541
279
421
60
486
415
283
385
240
338
370
289
349
0.1 mg/L
401
493
318
442
60
367
394
311
387
240
310
367
250
346
1 mg/L
427
481
307
464
60
367
374
246
368
240
259
355
195
303
5 mg/L
458
491
294
443
60
364
373
282
338
240
246
317
206
284
10 mg/L
416
483
323
410
60
298
375
281
349
■:-:-:•:•:•:-:•:•:•:-: .> v.v.»:.» x-:-:-:-:-:-:-----:-:-:-:-:-:-:-:-:
240
255
329
223
275
72
1000
Control
0.1 mg/L
-x-
1 mg/L
5 mg/L
— A-
10 mg/L
(a)
60 120 180
Time (minutes)
240
•Referenced to internal
standard, chlorobenzene
(b)
700
600
2 500
CL
Q.
— 400
S 300
c
m 200 -
100 -
Avg S.D. = 48.25 ppb
-O— Control
-B-0.1 mg/L
-A-1 mg/L
-X-5 mg/L
-*-10 mg/L
60 120
Time (minutes)
180
240
"Referenced to internal
standard, chtorobenzene
Figure 4-5. Benzene Concentration as a Function of Time and MB
Concentration in Sunlight; (a) pH=10, 1 = 542-696 W/m
(b) pH=7, I aVK = 665-891 W/m
73
500
(a)
— 0-
Control
-x-
0.1 mg/L
1 mg/L
— Q-
5 mg/L
-10 mg/L
60 120 180
Time (minutes)
240
"Referenced to internal
standard, chlorobenzene.
350
-O- Control
-B-0.1 mg/L
^A-1 mg/L
-X-5 mg/L
-X-10 mg/L
60 120
Time (minutes)
180
240
•Referenced to internal
standard, chkxobenzene
(b)
Figure 4-6. Toluene Concentration as a Function of Time and MB
Concentration in Sunlight; (a) pH =10, I avK = 542-696 W/m
(b) pH=7, I avg = 665-891 W/m 2
74
(a)
Q.
Q.
<D
c
0)
N
c
CO
-O- Control
-B-0.1 mg/L
^A-1 mg/L
^C^5 mg/L
-3K-10 mg/L
60 120 180
Time (minutes)
240
•Referenced to internal
standard, chlorobenzene
§ 500
2 400
c 300
a
m 200
100
(b)
Figure 4-7.
-I
Avg S. D. = 36.02 ppb
-♦—Control
-B-0.1 mg/L
-&-1 mg/L
-X-5 mg/L
-X-10 mg/L
60 120 180
Time (minutes)
240
•Referenced to internal
standard, chlorobenzene
Benzene Concentration as a Function of Time and RB
Concentration in Sunlight; (a) pH =10, T = 715-775 W/m 2
(b) pH=7, I avg = 746-856 W/m 2
(a)
100
75
Avg S. D. = 57.09 ppb
60 120 180
Time (minutes)
*♦— Control
-B-0.1 mg/L
-A-1 mg/L
"X~5 mg/L
^K^10 mg/L
240
•Referenced to internal
standard, chlorobenzene
600
(b)
60 120 180
Time (minutes)
— o-
Control
0.1 mg/L
1 mg/L
-*
5 mg/L
-10 mg/L
240
"Referenced to internal
standard, chlorobenzene
Figure 4-8. Toluene Concentration as a Function of Time and RB
Concentration in Sunlight; (a) pH =10, I avB = 715-775 W/m 2
(b) pH=7, I avg = 746-856 W/m 2
avg
76
Table 4-9. Normalized Benzene (±0.09) and Toluene (±0.11) Concentration
in MB Experiments
BENZENE
Sunlight pH 10
Sunlight pH 7
Dark pH 10
Dark pH 7
Control
N 60 /N
0.78
0.96
0.90
1.01
N 120 /N
0.59
0.86
0.75
0.87
0.1 mg/L
N 60 /N
0.77
0.88
1.02
0.83
N 240 /N„
0.67
0.80
0.68
0.77
1 mg/L
N 60 /N
0.86
0.85
0.72
0.79
1WN
0.71
0.80
0.59
0.71
5 mg/L
N 60 /N
0.87
0.76
0.95
0.90
N 240 /N„
0.77
0.65
0.65
0.75
10 mg/L
N 60 /N
0.75
0.92
0.98
0.81
N 240 /N
0.63
0.77
0.74
0.72
TOLUENE'''
SunlightpH 10
SunlightpH 7
Dark pH 10
DwfkpH7
Control
N 60 /N
0.70
0.88
0.85
0.99
N 120 /N
0.49
0.77
0.68
0.76
0.1 mg/1
I
N 60 /N
0.72
0.80
0.98
0.76
N 240 /N
0.57
0.57
0.58
0.63
1 mg/L
N 60 /N
0.82
0.77
0.66
0.71
N 240 /N
0.64
0.67
0.51
0.58
5 mg/L
N 60 /N
0.77
0.72
1.01
0.84
N 240 /N
0.64
0.54
0.55
0.63
10 mg/L
N 60 /N
0.70
0.85
0.92
0.78
N 240 /N
0.53
0.62
0.65
0.63
77
Table 4-10. Normalized Benzene (±0.06) and Toluene (±0.07) Concentration
in RB Experiments
BENZENE
Sunlight pH 10
Sunlight pH 7
Dark pH 10
Dark pH 7
Control
Neo/N,,
0.94
0.81
1.04
0.95
N 12( /N
0.68
0.74
1.02
0.86
0.1 mg/L
Neo/No
0.93
0.87
1.00
0.87
N 24( /N
0.85
0.77
0.71
0.81
1 mg/L
Neo/No
0.90
0.83
0.84
0.91
N 240 /N
0.65
0.81
0.71
0.78
5 mg/L
Neo/N,,
0.84
0.82
1.00
0.81
N 24( /N
0.64
0.73
0.81
0.69
10 mg/L
Neo/No
0.72
0.85
0.90
0.95
N 240 /N
0.66
0.74
0.77
0.75
TOLUENE
Sunlight pH 10
SuniightpHf
Dark pH 10
DarkpH7
Control
Neo/No
0.86
0.82
1.01
0.94
N I2( /N
0.58
0.69
1.03
0.81
0.1 mg/L
Neo/No
0.89
0.83
0.99
0.89
N 240 /N
0.76
0.71
0.65
0.75
1 mg/L
Neo/N
0.87
0.79
0.78
0.89
N 240 /N
0.59
0.73
0.65
0.71
5 mg/L
Neo/No
0.78
0.53
0.78
0.96
0.69
0.78
N 240 /N
0.64
0.61
10 mg/L
Neo/No
0.71
0.82
0.87
0.91
N 240 /N
0.62
0.65
0.69
0.65
78
(a)
60 120 180
Time (minutes)
240
* Referenced to internal
standard, chlorobenzene
O No MB, Sunlight
-O-NoMB, Dark
^^0.10 mg/L, Sunlight
-K- 0.10 mg/L, Dark
^ 0.60
o
0.40
0.20
0.00
Avg S. D. = 0.04
60 120 180
Time (minutes)
240
* Referenced to internal
standard, chkxooenzene
-O^No MB, Sunlight
-©—No MB, Sunlight
0.1 mg/L, Sunlight
■0.1 mg/L, Dark
(b)
Figure 4-9. Normalized Benzene Concentration in Sunlight with 0.1 mg/L
MB, (a) pH =10, I avg = 542-696 W/m 2 (b) pH=7, 1 = 665-891 W/m
79
(a)
1.00 I
0.90
0.80
0.70
0.60
o
o
0.50
0.40
0.30
0.20
0.10
On
Avg S.D. = 0.07
C
) 50 100 150
Time (minutes)
200
* Referenced to internal
standard, chlorobenzene
A
No MB, Sunlight — Q— 0.1 mg/L,
Sunlight
V
Dark
X
imo Mb, uarK a u.n mg/L,
1.00
0.90
0.80
0.70
0.60
o
o
0.50
0.40
0.30
0.20
0.10
0.00
60 120
Time (minutes)
180
240
* Referenced to internal
standard, chlorobenzerte
No MB, Sunlight
-No MB, Dark
+
0.1 mg/L, Sunlight
-0.1 mg/L, Dark
(b)
Figure 4-10. Normalized Toluene Concentration in Sunlight with 0.1 mg/L
MB; (a) pH =10, T = 542-696 W/m 2 (b) pH=7, I avE = 665-891 W/m
80
(a)
1.20
0.20
0.00
Avg S.D. = 0.28
4-
60 120 180
Time (minutes)
240
'Referenced to internal
standard, chlorobenzene
-O^No MB, Sunlight
-O— No MB, Dark
-B— 0.1 mg/L, Sunlight
-H — 0.1 mg/L, Dark
o
o
1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
Avg S. D. = 0.05
60 120
Time (minutes)
180
240
'Referenced to internal
standard, chiorobenzene
■No MB, Dark
No MB, Dark
-H — 0.1 mg/L, Sunlight
-O— 0.1 mg/L, Dark
(b)
Figure 4-11. Normalized Benzene Concentration in Sunlight with 0.1 mg/L
RB, (a) pH =10, 1 = 715-775 W/m 2 (b) pH=7, 1 = 746-856 W/m 2
avg
81
(a)
60 120 180
Time (minutes)
240
•Referenced to internal
standard, chlorobeneene
No MB, Sunlight
-No MB, Dark
0.1 mg/L, Sunlight
-0.1 mg/L , Dark
240
Time (minutes)
'Referenced to internal
standard, chlorobenzene
-No MB, Sunlight
No MB. Dark
1 mg/L, Sunlight
01 mg/L, Dark
(b)
Figure 4-12. Normalized Toluene Concentration in Sunlight with 0.1 mg/L
RB, (a) pH =10, I avK = 715-775 W/m 2 (b) pH=7, I ave = 746-856 W/m 2
avg
Data Analysis bv ANOM
Initial observation of the disinfection data for dye photosensitization
suggested that photochemical destruction may have taken place.
Therefore, these data were selected for additional analysis by ANOM. The
fractional survival of colony forming units (cfu) after 5 minutes, 15 minutes
and 30 minutes were all analyzed in this manner, for both MB and RB
experiments. An a-level of 0.05 was used for all data presented.
ANOM was used to examine the controlled parameters for the
experiments, presence or absence of sunlight, pH level, and dye
82
concentration. The presence and absence of sunlight appeared to be the
most significant factor in both MB and RB experiments, based upon the
ANOM.
Grand averages were calculated separately for the MB and RB data
at 5, 15 and 30 minutes using fractional survival of cfu. The grand
averages calculated for MB experiments were 0.39 (±0.14), 0.28 (±0.13) and
0.23 (±0.13) for 5, 15 and 30 minutes, respectively. Both the grand averages
and average standard deviations were slightly higher for the RB
experiments with grand average values of 0.71 (±0.19), 0.61 (±0.24) and 0.47
(±0.16), respectively, for 5, 15, and 30 minutes. The general values
calculated for use in ANOM are given in Table 4-11.
Table 4-11. Calculated ANOM Values for Dye Photosensitized Disinfection
Sample Set
Grand Average,
X
Avg Std Dev
Avg Range
SD(X)
RB @ t=5 minutes
0.71
0.19
0.46
0.23
RB @ t=15 minutes
0.61
0.24
0.57
0.27
RB @ t=30 minutes
0.47
0.16
0.36
0.21
MB @ t=5 minutes
0.39
0.14
0.31
0.20
MB @ t=15 minutes
0.28
0.13
0.31
0.18
MB @ t=30 minutes
0.23
0.13
0.30
0.18
Effect of Sunlight
The data from each sample set (5, 15 and 30 minutes) were separated
into two subgroups, based on the absence and presence of sunlight. This
gave an n value of 30 samples per subgroup and a k value of 2 subgroups for
each sample set. The n and k values were used to determine the degrees of
freedom, v, bias correction factor, d/, and , subsequently, ANOM critical
value, H, from the bias correction factor and critical values tables (Wheeler
83
1990). The corresponding values were v = 33.5, d/ = 4.116, and, for an a =
0.05, H = 1.44. These values, along with the values in Table 4-11, were used
to determine the decision limits as shown in Equations 4-4 to 4-6.
For each subgroup, in this case sunlight and dark, an average was
calculated and plotted on a chart with the decision limits. The subgroup
averages for sunlight in both the MB and RB experiments are shown in
Table 4-12. As noted previously, a subgroup average outside of the decision
limits indicated a parameter was statistically significant. As shown below
the absence or presence of sunlight was found to be statistically significant
in all cases tested for both MB (Figure 4-13) and RB (Figure 4-14)
experiments.
Table 4-12. Sunlight Subgroup Averages for Dye Photosensitized
Disinfection; Values are Fractional Survival of E. coli
MB Subgroup
Sunlight (542
■ 891 W/m 2 )
Dark
X
S
R
X
S
R
t = 5 minutes
t = 15 minutes
t = 30 minutes
0.282
0.141
0.038
0.064
0.069
0.033
0.139
0.153
0.075
0.501
0.454
0.420
0.212
0.196
0.227
0.479
0.461
0.528
RB Subgroup
Sunl
ight(715
• 856 W/m 2 )
Dark
X
S
R
X
S
R
t = 5 minutes
t = 15 minutes
t = 30 minutes
0.598
0.371
0.132
0.224
0.231
0.146
0.518
0.541
0.330
0.830
0.850
0.802
0.166
0.253
0.165
0.396
0.595
0.390
84
(a)
0.55
0.50
0.45
>Dark
UDL = 0.44
40 -I 1 Grand Av JL
1 T 0~352
0.35 4
z 0.30
0.25
0.20
0.15 4-
0.10
LDL = 0.34
Sunlight
(542 - 891
W/m 2 )
"
-UDLxbar
-LDLxbar —
■-Gavg
-Light
(b)
0.50
0.45
0.40
0.35
0.25
0.20
0.15
0.10
UDL = 0.35
■> 0.30 I J.
LDL = 0.25
•UDLxbar-
Dark
Grand Avg
— D-2S7 -
Sunlight
(542 - 891
W/m 2 )
-LDLxbar Gavg ♦ Light
0.40
UDL = 0.38
♦ Dark
0.35 -
/
0.30
/
0.25 ■
0.20 -
-/--
Grand Avg
0.23
0.15
/
0.10
0.05
00
LDL = 0.08
/ Sunlight
f (542 - 891
W/m 2 )
-UDLxbar-
-LDLxbar Gavg
"Light
(C)
Figure 4-13. Significance of Sunlight, Based on ANOM, in MB Experiments
(a) 5 Minutes (b) 15 Minutes (c) 30 Minutes
85
(a)
0.90
0.80
0.70
0.60
?0.50
■0.40
0.30 4
0.20
0.10
0.00
UDL = 0.77 »Dark
/Sunlight
LDL = 0.65 «f(715-856
W/m 2 )
Grand Ave
— o~7r
-UDLxbar-
-LDLxbar Gavg '
-Light
(b)
UDL = 0.68
? 0.50
0.40
0.30
0.20
0.10
LDL = 0.54
-UDLxbar-
Dark
0.90
0.80
0.70
Grand Av ;
Sunlight
(715-856
W/m 2 )
-LDLxbar Gavg
-Light
(O
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
UDL = 0.52
LDL = 0.41
Dark
Grand Avg
Sunlight
(715-856
W/m 2 )
-UDLxbar ■
-LDLxbar Gavg — ♦—Light
Figure 4-14. Significance of Sunlight, Based on ANOM, in RB Experiments;
(a) 5 Minutes (b) 15 Mintues (c) 30 Minutes
86
Effect of pH
As was done for evaluation of the effect of sunlight, the data from
each sample set (5, 15 and 30 minutes) were separated into two subgroups,
based upon the pH value of 7 or 10. Since k and n were the same, and the
same a-level was used, the values for v, d/ , and H were also the same.
Again, these values, along with the values in Table 4-11, were used to
determine the decision limits as shown in Equations 4-4 to 4-6.
For each subgroup, in this case pH=7 and pH=10, an average was
calculated and plotted on a chart with the decision limits. The subgroup
averages for pH are shown in Table 4-13. ANOM charts are shown in
Figures 4-15 and 4-16.
Table 4-13. pH Subgroup Averages for Dye Photosensitized Disinfection.
Values are Fractional Survival of E. coli.
MB Subgroup
pH =
:10
pH = 7
X
s
R
X
s
R
t = 5 minutes
t = 15 minutes
t = 30 minutes
RB Subgroup
0.38
0.31
0.21
0.09
0.07
0.10
:,_
0.20
0.15
0.23
0.40
0.28
0.25
0.34
0.19
0.35
0.76
0.46
0.83
X
S
R
X
s
R
t = 5 minutes
t = 15 minutes
t = 30 minutes
0.78
0.69
0.55
0.07
0.16
0.12
0.16
0.37
0.27
0.65
0.54
0.38
0.26
0.32
0.19
0.63
0.76
0.45
87
0.50
0.45
0.40
0.35
0.30
0.25
-UDL = 0.44
■;
^XpH 7 Grand Avg
~">CpH10" °" 39
LDL = 0.34
(a)
■UDLxbar ■
■LDLxbar Gavg — K — pH
(b)
0.40
0.38
0.36
0.34
0.32
0.30
0.28
0.26
0.24
0.22 4
0.20
UDL = 0.35
\dH 10
^CpH7
Grand Avg
Tr.3o-
LDL = 0.25
■UDLxbar-
■LDLxbar Gavg — K — pH
(O
0.50
0.45
0.40
0.35
o 0.30
1 0.25
2 0.20
0.15
0.10
0.05
0.00
UDL = 0.38
JXpH 7_ _Grand Avg
yfH10 "D.73
- LDL = 0.08
-UDLxbar
-LDLxbar Gavg — X — pH
Figure 4-15. Significance of pH, Based on ANOM, in MB Experiments; (a) 5
Minutes (b) 15 Minutes (c) 30 Minutes
88
(a)
1.00
0.90
0.80
;0.70
0.60
0.50
040
UDL = 0.77
tUh 1 (
\ Grand Avg g
LDL = 0.65
pH^f-
-UDLxbar •
-LDLxbar Gavg — X — pH
(b)
UDL = 0.68
0.80
0.75
0.70 4-
0.65
o 0.60 -f
\ 0.55
0.50
0.45
0.40
0.35 j
0.30 -L
LDL = 0.54
Grand Aye
0.61
p+tT 1 -
-UDLxbar ■
-LDLxbar Gavg — M — pH
0.60
0.50
0.40
o
^,0.30
0.20
0.10
000
UDL = 0.52
XjdH 10
\—
Grand Ave
" LDL = 0.41
VpH 7
-■
-UDLxbar
•LDLxbar Gavg — X — pH
(0
Figure 4-16. Significance of pH, Based on ANOM, in RB Experiments; (a) 5
Mintues (b) 15 Minutes (c) 30 Minutes
89
It is clear that pH was statistically insignificant in MB experiments.
This was inconsistent with the findings of Eisenberg et al. (1987), who
reported a very strong correlation with pH values and more efficient MB
inactivation at a basic pH.
The ANOM tests were somewhat inconclusive for RB experiments.
The data suggested that a neutral pH of 7 was slightly more effective for
disinfection than the basic pH of 10; however, since the a-level used for
determination of critical values was 0.05, it was possible that the signals
were false and, therefore, not significant.
Effect of Dye Concentration
For evaluation of the effect of the concentration of MB and RB, the
data from each sample set (5, 15 and 30 minutes) were separated into five
subgroups, based upon the concentration of dye. This gave an n value of 12
samples per subgroup and a k value of 5 subgroups for each sample set.
The n and k values were used to determine the degrees of freedom, v, bias
correction factor, d 2 \ and, subsequently, ANOM critical value, H, from the
bias correction factor and critical values tables (Wheeler 1990). The
corresponding values were v = 44.1, d/ = 3.276, and, for an a = 0.05, H =
2.39. These values, along with the values in Table 4-11, were used to
determine the decision limits as shown in Equations 4-4 to 4-6.
For each subgroup an average was calculated and plotted on a chart
with the decision limits. The subgroup averages for dye concentrations in
both the MB and RB experiments are shown in Table 4-14. As shown in
Figure 4-17, signals were obtained for the control reactor on the upper side,
90
and for 5 and 10 mg/L of MB on the lower side, indicating that the absence
or presence of MB was significant at both 5 and 15 minutes. However, by 30
minutes (Figure 4-17c), the presence of MB was no longer of significance,
and disinfection in sunlight alone was just as effective.
The presence of RB, however, in any concentration, did not appear to
differ significantly from the absence of RB, suggesting that it neither
enhanced nor detracted from the photolytic disinfection (Figure 4-18).
Since MB concentration displayed some significance, each of the
subgroup averages at 5 minutes was plotted against the control and the
high concentration (10 mg/L) to determine the minimum significant
concentration. These combinations allowed for the determination of
optimum concentration range for the fastest disinfection. There were
again two subgroups, for a k of 2, with the n value (samples per subgroup)
remaining at 12. The corresponding table values were v = 17.8, d/ = 3.304,
and, for an a = 0.05, H = 1.5.
Table 4-14. Dye Concentration Subgroup Averages in Disinfection
Experiments. Values are Fractional Survival of E. Coli.
MB
Ctrl
0.1 mg/L
1 mg/L
5 mg/L 10 mg/L
X
S
R
X s R
X s R
X s R X s R
5
15
30
0.90
0.64
0.47
0.23
0.21
0.28
0.52
0.48
0.65
0.54 0.13 0.30
0.40 0.17 0.41
0.36 0.20 0.48
0.38 0.13 0.29
0.31 0.13 0.31
0.25 0.08 0.18
0.10 0.14 0.31 0.04 0.06 0.13
0.09 0.10 0.23 0.04 0.05 0.11
0.05 0.07 0.14 0.02 0.02 0.05
RB
Ctrl
0.1 mg/L
1 mg/L
5 mg/L 10 mg/L
X
S
R
X s R
X S R
X s R X s R
5 0.82 0.18 0.43 0.68 0.25 0.58 0.66 0.24 6.56 0.73 0.16 6.38 0.70 6.15 0.34
15 0.64 0.28 0.66 0.55 0.30 0.72 0.60 0.25 0.53 0.70 0.18 0.44 0.56 0.20 0.47
30 0.52 0.15 0.35 0.48 0.17 0.40 0.44 0.21 0.49 0.48 0.12 0.27 0.42 0.13 0.29
91
(a)
1.00
Control
0.40
0.30
020 f LDL = 0.26
0.10
0.00
Grand Avg
10 mg/L
-UDLxbar
■LDLxbar Gavg B MB Cone
(b)
0.70
0.60
0.50 -
[Control
0.40
0.30
0.20
UD = 0.4
0.10 4- LDL = 0.17
0.00
mg/L Grand Avg
^ CT3U--
10 mg/L
-UDLxbar-
-LDLxbar Gavg — B MB Cone
(C)
0.50
0.40
0.30
0.20
0.10
0.00
-0.10
-UDL = 0.47
^Control
DJ mg/L
>1 mall Grand Avg
-■
\ — 0~23 -
^ a -« 10 mg/L
LDL = 0.01
■UDLxbar'
-LDLxbar Gavg — B— MB Cone
Figure 4-17. Statistical Significance of MB Concentration, Based on ANOM,
on Disinfection in Sunlight; (a) 5 Minutes (b) 15 Minutes (c) 30
Minutes
1.00
0.90
0.80
0.70
0.60
0.50
0.40 +■
0.30
0.20
UDL = 0.87
OXontrol
UK fT
HlLin 0fl
^O-LJT
fl^lmg/L
~*-T0Trtg7r
- LDL = 0.56
-
0.71
(a)
-UDLxbar-
-LDLxbar Gavg
-MB Cone
(b)
1.00
0.90
0.80
0.70
o
5 0.60
z
0.50
0.40
0.30
0.20
UDL = 0.80
mg/L
LDL = 0.42
Grand Avg
— C.61
■UDLxbar ■
-LDLxbar Gavg
-MB Cone
(0
0.70
0.60
0.50
: 0.40
! 0.30
0.20
0.10
0.00
UDL = 0.61
LDL = 0.32
;, Grand Avg
0-47"*
10 mg/L
-UDLxbar-
-LDLxbar Gavg —a RB Cone
Figure 4-18. Statistical Significance of RB Concentration, Based on ANOM,
on Disinfection in Sunlight; (a) 5 Minutes (b) 15 Minutes (c) 30
Minutes
98
As noted previously, a subgroup average outside of the decision limits
indicated a parameter was statistically significant. When all of the MB
concentrations were considered, the presence of at least 5 mg/L MB showed
significance up to 30 minutes. By 30 minutes, the presence of MB no longer
had an impact on the destruction of E. coli. The presence of RB was not
significant in any instance, as was anticipated from the initial
observations.
In order to determine the minimum effective MB concentration, the 5
minute subgroup averages were plotted against the control, and then,
selectively, against each other. Every concentration showed significance
relative to the control, suggesting that all concentrations contribute to
photodynamic action. When examined relative to 10 mg/L, all
concentrations except 5 mg/L showed a significant difference, suggesting
that an increase in effectiveness occurred with increases in MB
concentration up 5 mg/L.
■UDLxbar-
■LDLxbar Gavg '
■MB Cone
Figure 4-19. Comparison of Disinfection Efficacy of Control and 0.1 mg/ L
MB in Sunlight at 5 minutes, Based on ANOM
94
z
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
Contror
UDL = 0.71
Grand Avg
--
0.63
LDL = 0.54
\
-
TD 1 mg/L
--
■UDLxbar
■LDLxbar Gavg
■MB Cone
Figure 4-20. Comparison of Disinfection Efficacy of Control and 1 mg/L MB
in Sunlight at 5 minutes, Based on ANOM
5
0.70
0.60
0.50
0.40
0.30 4
0.20
0.10
0.00
^Control
UDL = 0.45 \
\
Grand Avg
_-
0.36
LDL = 0.28
\
a 5 mg/L
-UDLxbar
-LDLxbar Gavg
-MB Cone
Figure 4-21. Comparison of Disinfection Efficacy of Control and 5 mg/L MB
in Sunlight at 5 minutes, Based on ANOM
95
z
5
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
\
OTitrol—
UDL = 0.56
--
Grand Avg
0.47
LDL = 0.38
--
D 10 mg/L
-UDLxbar
-LDLxbar Gavg
■MB Cone
Figure 4-22. Comparison of Disinfection Efficacy of Control and 10 mg/L
MB in Sunlight at 5 minutes, Based on ANOM
0.60
0.50
0.40
I 0.30
2
0.20
0.10
0.00
0.1 mg/L
UDL = 0.38
Grand Avg
~~D^0" -
LDL = 0.20
10 mg/L
■UDLxbar
■LDLxbar Gavg
•MB Cone
Figure 4-23. Comparison of Disinfection Efficacy of 0.1 mg/ L and 10 mg/L
MB in Sunlight at 5 minutes, Based on ANOM
96
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
UDL = 0.30
*1 mg/L
1 Grand Avg
_i cr21
LDL = 0.12
*10 mg/L
■UDLxbaf
-LDLxbar Gavg — X — MB Cone
Figure 4-24. Comparison of Disinfection Efficacy of 1 mg/ L and 10 mg/L
MB in Sunlight at 5 minutes, Based on ANOM
0.20
0.15
0.10
^ 0.05
H 5 m 9 /L Grand Av£
0.00
UDL = 0.15
X10
mg/L
"oTBT"
-0.05 | LDL = -0.02
-0.10
■UDLxbar-
■LDLxbar Gavg — X — MB Cone
Figure 4-25. Comparison of Disinfection Efficacy of 5 mg/ L and 10 mg/L
MB in Sunlight at 5 minutes, Based on ANOM
When the data were viewed graphically (Figure 4-26), a significant
correlation was seen between the concentration of MB and disinfection,
which was confirmed by linear regression. At the tested concentrations an
increase in the MB concentration led to a direct increase in the effectiveness
of disinfection with time. The strongest correlation was found with the MB
concentration and ln(N t /N ). A linear fit gave an r 2 of 0.94, with p-values of
97
0.02 and 0.01 for the intercept and slope, respectively, for t=5 minutes
(Figure 4-27).
Acher and Juven (1977) reported that an increase in MB
concentration from 0.5 to 5.0 mg/L caused an increase in the inactivation of
coliform in both sewage water and tap water in sunlight. They also
reported that 10 mg/L of RB was required to achieve the same disinfection
effect as 4 mg/L MB, although no relationship of RB concentration and
disinfection was reported. The results found in this experiment were
consistent with those reported by Acher and Juven (1977) with regard to
destruction of E. Coli by MB.
1.00 a
0.90 -
0.80
"
0.70 -
0.60 -
5 0.50 <
_
2 0.40 -
0.30
0.20
^^^^ __
0.10 -
00 '
0.00
0.10 1.00 5.00
10.
mg/L Meth
/lene Blue
Figure 4-26. Fractional Survival of E. coli in sunlight at t=30 minutes as a
Function of MB Concentration; Bars are One Standard Deviation
Effect of Initial Coliform Density
As shown in Table 4-2 the initial coliform density varied broadly
between experiments. The variations seen across experiments were also
present, though to a lesser extent, within each experimental set.
98
Analysis of the data indicated no significant correlation of initial
coliform density with fractional survival (N t /N ) at time t for either dye. The
typical relationship, based on the mean values from all experiments, is
shown for both MB (Figure 4-28) and RB (Figure 4-29).
ooo 4
_ 050 y = -0.28x- 0.5175
>\ R 2 = 0.94
-1.00
*>w
2-1.50
■2.
~ -2.00
-2.50
• ^V.
-3.00
^\n
-3 50
0.00 2.00 4.00 6.00 8.00 10.00
mg/L Methylene Blue
O LN(N5/N0) Regression, ln(N5/N0)
Figure 4-27. Least Squares Regression of Natural Logarithm of Fractional
Survival of E. coli as a Function of MB Concentration at t=5
Minutes (p-values for intercept and coefficient are 0.02 and 0.01,
respectively)
1.00
0.90
0.80
D
a
0.70
□
0.60
0.50
n
D
0.40 -
?~*
a
0.30 -
a
0.20 -
0.10
0.00
dRj
B
n
a
c
500
1 000 1 5(
Initial Colony Count, cfu/L
x 10 3
Figure 4-28. Initial Colony Count vs. Fractional Survival of E. coli at t=60
Minutes for MB Experiments
■s
83
it
o
>.
c
o
o
o
200
000
800
600
400
200
o
o
**
— I —
500 1000 1500
Initial Colony Count (cfu/L x 10 3 )
2000
Figure 4-29. Initial Colony Count vs. Fractional Survival of E. coli at
t=30 Minutes in RB Experiments
Correlation of initial coliform density with disinfection rate has not
been reported in the literature for dye photosensitization. The indication,
from the results of these experiments, was that no true correlation exists.
This is consistent with the findings of Ti0 2 photocatalysis reported in this
chapter.
Reactor Efficacy
After numerous iterations of reactor configurations with no evidence
of destruction of chemical contaminants, the question of the effectiveness of
the reactor and/or reaction process arose. Examination of the problem led
to several possibilities for ineffectiveness of the reactor or reaction process:
• dye concentrations were not consistent with previous work
• reactor was not transparent to light of appropriate wavelengths;
• dye used was not photoactive.
100
Consistency with previous work
In order to provide confidence in the reactor system, a set of
experiments was conducted which reproduced results found in the
literature. Eisenberg et al. (1987) were able to destroy bromacil in
wastewater with MB in sunlight under a variety of pH conditions using
several MB concentrations. While these experiments did not attempt to
duplicate the work conducted by Eisenberg et al., there was a desire to
ensure that similar results could be obtained using the photosensitization
reactor design. Photosensitization of water containing bromacil with 10
mg/L MB resulted in a 75% reduction, from 1448 ppb (±218) to 358 ppb
(±48.5), after four hours of irradiation in sunlight versus a 13% reduction,
to 1265 ppb, for the control reactor with no MB.
Transparency of reactor.
Disinfection of E. coli occurred in all reactors tested in the sunlight,
but not in the reactors tested in the dark in both the MB and RB
experiments. This disinfection occurred, albeit at different rates, both in the
presence and absence of dye. Were the reactors not transparent to sunlight,
there would have been no difference in disinfection between the reactors
run in sunlight and those held in the dark chamber.
Photoactivity of dyes
Observation of the reactors in sunlight provided visual evidence of the
photoactivity of the dyes. Methylene blue and, to a lesser extent rose bengal,
began to self-destruct in sunlight. The disappearance of the dye suggested
clearly that the dye was photoactive, as this was the behavior anticipated by
the photoactive dye (Schlauch 1987). Indeed, the fact that the dye would
101
eventually react with itself was one of the features which made it attractive
as a water treatment photochemical.
Summary
Of the systems tested in these experiments, photosensitized
disinfection with methylene blue was the only process which yielded
positive results. While disinfection did occur in the presence of rose bengal,
it did not enhance the reaction to any degree. There were no indications at
all that photosensitization occurred with respect to the chemical
contaminants with either methylene blue or rose bengal. Consequently,
with the exception of methylene blue photosensitized disinfection, these
processes did not show promise for application.
Initial results indicate promise for methylene blue disinfection;
however, before the process is viable, additional, application specific,
research is required. The positive aspects were pH and dosage of MB.
Since pH was not a significant factor, no adjustments would be required for
use of MB as a disinfectant. While dosage was of some importance, it
would not require tight control.
One drawback to the use of MB as a disinfectant for drinking water
was the presence of color. While all of the MB disappeared from reactors at
the lower dosages, by the end of a four hour experiment, some slight color
was still visible at the higher dosages (5 and 10 mg/L). The color in the
water would likely be a deterrent for use as drinking water, particularly if
the water was clear prior to treatment. In most cultures there is an
expectation that ingested substances be visually appealing, including
colorless water.
102
Most importantly, however, in order for this process to be determined
feasible for application, it must be tested over a much broader range of
microbiological contaminants. Site specific testing is a must, as species
may differ from one locale to the other. Additionally, the process would
need to be tested for inactivation of viruses and cysts.
While the addition of MB did increase the rate of disinfection over
sunlight alone, the advantage may not be enough to justify the addition of a
foreign substance into a drinking water system, no matter how benign.
Photocatalvsis with Titanium Dioxide
Laboratory experiments were conducted to determine the effects of
Ti0 2 concentration and pH on the destruction of bacteria (Escherichia coli,
Pseudomonas aeruginosa, and Serratia marcescens) and aromatic
hydrocarbons (benzene, toluene, and xylene) under UV light. As described
in Chapter 3 the experiments were conducted under the following
conditions:
• UV lamps and dark,
• pH 4 and pH 7,
• 0.01, 0.05 and 0.10% Ti02.
Initially, two experimental sets were conducted, to ensure
reproducibility of the results. A complete set of experiments were
represented by two reactors for each of the sets of conditions highlighted
above, for a total of 32 reactors per set. Eight reactors were run at a time,
every two reactors containing a different concentration of Ti0 2 , with all
other parameters the same. A third set was conducted to collect additional
103
chemical analysis data; however, no microbiological data were collected
from this set. The chemical analysis results were reported from the final
set, and the disinfection results were reported from the first two sets.
In the first experimental set, samples were taken directly onto agar
plates from each reactor at time intervals of 0, 15, 30, 60, 120 and 240
minutes. Two replicates were plated from each sample for immediate
microbiological analysis. A second sample was taken at 0, 120 and 240
minutes directly into headspace vials, refrigerated and saved for chemical
analysis. In the second experimental set, samples were taken from the
reactor at time intervals of 0, 30, 60 and 120 minutes with the same
treatment as stated above. The samples for chemical analysis were taken
at 0, 60 and 120 minutes directly into headspace vials, refrigerated and
saved for chemical analysis.
The third set of experiments was conducted because complete
destruction of all chemical components was observed in almost all of the
second samples in each of the first two experimental sets, making trend
detection impossible. Samples were taken at 0, 5, 15, 30 and 60 minutes and
refrigerated immediately.
For the experiments conducted under UV lamps, the lamp intensity
was measured and recorded in the light chamber to be approximately 29
W/m 2 when the chamber door was closed. The dark experiments were
conducted in the same chamber with the lights turned off.
Disinfection results were reported as aggregate colony forming units
and fractional survival of total bacteriological colonies for all species
present. Results for detoxification of aromatic hydrocarbon compounds
104
were reported by individual component with the exception of m-xylene and
p-xylene. The two isomers eluted too closely for separate peak
identification, therefore, the results were reported as one component.
The data, as well as the impact of each of the measured and
controlled parameters, are explored in more detail below, and results are
compared with published data on Ti0 2 photocatalysis of BTEX and Ti0 2
photocatalyzed disinfection.
General Comments About Experimental Data
The average standard deviation of the disinfection data was 12% as
calculated from fractional survival values. Plates on which the colonies
were not individually identifiable and those with severe contamination were
not counted, which resulted in the loss of approximately 50% of the plates in
a given experimental set. The difficulties encountered in microbiological
analysis that resulted in such a high loss rate and large standard deviation
were attributed to three factors: 1) use of mixed cultures, 2) extremely high
initial colony densities, and 3) inexperience of the experimenter in
microbiological techniques.
In the first experimental set, very few values were obtained from the
intermediate samples at 15, 30 and 60 minutes. The colony densities were
much too high for differentiation of the data.
The average standard deviations of the detoxification data ranged
from 6-9% of the average values, with o-Xylene having the highest. No
sample loss occurred for detoxification. Chemical samples were analyzed
within approximately two weeks of the experiment.
105
Statistical Treatment of the Data
The data were treated as outlined previously in the section on dye
photosensitization. No specific adjustments were required for the Ti0 2
disinfection data with the exception of normalizing negative percentages of
destruction to zero. There were two samples in chemical data thought to be
outliers; however, since only two replicates existed, outlier detection was
not possible.
Presentation of Results and Identification of General Trends
Ti0 2 photocatalysis was effective for simultaneous detoxification of
aromatic hydrocarbons and disinfection of the mixed bacterial species
tested over a range of conditions. The most destruction of both
bacteriological and chemical contaminants occurred in the presence of U V
light with 0.01% Ti0 2 ; however, disinfection seemed to be more effective at a
pH of 4, and detoxification appeared to fare better at pH 7.
Complete disinfection was achieved in one hour with 0.01% Ti0 2 at
pH 4. Complete disinfection within one hour was not observed in any other
reactor, where photocatalytic destruction of cfu ranged from 78% with
0.01% Ti0 2 at pH 7, to 92% observed with both 0.05% at pH 4 (Figure 4-30a)
and 0.10% Ti0 2 at pH 7 (Figure 4-30b). Complete disinfection was achieved
by four hours with both 0.01% and 0.05% Ti0 2 at pH 7.
Less than 60% reduction of cfu was attained in the control reactors by
four hours of irradiation under the UV lamps, and no persistent
destruction was observed in the dark reactors either with or without Ti0 2 .
The data are presented as mean fractional survival of bacteria in Table 4-15.
106
(a)
100
Time (minutes)
200
Ti0 2 Conc.
-6- 0.00%
-Q- 0.01 %
-A- 0.05%
-X-0.10%
1.60
(b)
0.00 J
100 200
Time (minutes)
Tip; Cone.
^-0.00%
Q-0.01%
A- 0.05%
0.10%
Figure 4-30. Ti0 2 Photocatalytic Disinfection in UV Light (29 W/m 2 ); Error
Bars are One Standard Deviation; (a) pH = 4 (b) pH = 7
The presence of Ti0 2 in reactors irradiated under ultraviolet lamps
resulted in some destruction of all of the aromatic hydrocarbons tested at all
concentrations. Photocatalytic destruction of all of the components to below
the detectable limits was observed in one reactor, reactor 4, by 60 minutes.
This reactor contained 0.01% Ti0 2 and water adjusted to a pH of 7. Figure
4-31 is a graphical representation of this reactor and its redundant reactor
(reactor 3), which was treated with the same conditions.
An examination of Table 4-16 shows that photocatalytic detoxification
took place under all conditions; however, by 60 minutes, only 50%
107
destruction of benzene was seen with 0.10% Ti0 2 at pH=4 and only 30% at
pH=7 (Figure 4-32). These values are fairly consistent for all of the
components as shown in Figures 4-33 and 4-34. Virtually no destruction of
any of the components in the absence of Ti0 2 or in the absence of light was
observed.
Table 4-15.
Mean Fractional Survival of Bacteria in
Ti0 2 Experiments
UV Light pH 4
UV Light pH 7
Dark pH 4
Dark pH 7
Control
Mean
Std Dev
Mean
Std Dev
Mean
Std Dev
Mean Std Dev
N 15 /N
-
-
-
-
0.63
0.00
-
-
N 30 /N
-
-
1.48
0.08
0.56
0.24
0.77
0.20
N 60 /N
-
-
1.15
0.10
0.41
0.25
0.77
0.08
N 120 /N
0.62
0.18
0.89
0.07
0.95
0.29
0.88
0.03
N 240 /N
0.42
0.25
0.77
0.03
1.51
1.25
1.14
0.17
0.01% Ti0 2
N 15 /N
0.33
0.00
-
-
-
-
.
-
N 30 /N
0.05
0.00
-
-
0.36
0.08
0.88
0.00
N 60 /N„
0.00
0.00
0.21
0.08
0.29
0.09
0.74
0.00
N 120 /N
0.00
0.00
0.06
0.02
1.06
0.24
0.85
0.11
N 240 /N
0.00
0.00
0.00
0.00
2.15
0.02
1.88
0.15
0.05% Ti0 2
N 15 /N
-
-
.
.
-
-
.
N 30 /N
0.26
0.03
0.59
0.11
0.59
0.12
0.62
0.05
N 6 „/N
0.08
0.01
0.22
0.01
0.61
0.01
0.98
0.32
N 120 /N
0.03
0.00
0.11
0.04
0.81
0.08
1.09
0.47
N 240 /N
0.09
0.08
0.00
0.00
1.04
0.17
1.63
0.33
0.10% Ti0 2
N 15 /N
-
-
-
-
-
-
-
.
N 30 /N
-
-
0.18
0.08
0.78
0.05
0.45
0.02
N 60 /N
0.18
0.06
0.08
0.02
1.22
0.29
0.49
0.05
N 120 /N
0.23
0.16
0.07
0.04
0.99
0.31
1.11
0.24
N 240 /N
0.12
0.13
0.09
0.11
1.21
0.29
1.26
0.08
108
Table 4-16
. Mean Concentration of BTEX (ppb) in Ti0 2 Experiments
1
BENZENE
UV yght P H 4
UV Light
Dark pH 4
Dark pH 7
0.00% TiO,
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
765
7
924
8
922
72
935
17
5min
813
46
895
26
1008
90
1019
25
15 min
825
22
956
41
891
14
1029
23
30min
769
38
901
16
828
6
1004
60 min
372
355
907
36
882
22
1068
69
0.01% TiO,
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
753
36
957
6
860
68
1009
19
5 min
466
84
264
24
853
2
1069
14
15 min
250
47
78
8
581
323
1052
21
30 min
63
20
23
3
727
10
1016
1
60 min
5
1
1
754
72
1010
68
0.05% TiO,
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
867
35
967
14
865
6
1042
39
5 min
706
23
707
206
863
10
1070
27
15 min
488
35
626
174
838
84
1110
27
30 min
267
102
448
122
689
60
1088
1
60 min
187
69
255
69
812
48
1075
1
0.10% TiO,
I AVg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
853
8
840
14
876
17
976
108
5 min
790
71
902
27
901
9
985
83
15 min
706
49
797
14
873
12
958
45
30 min
629
10
661
30
756
10
1005
53
60 min
521
33
602
11 842
10
NMMMMMMOMMMMM
988
79
UV Light pH 4
UV Light pH 7
Dark
P H4
Dark
P H7
0.00% Ti0 3
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
478
2
484
13
738
67
685
20
5 min
503
14
491
24
848
60
745
35
15 min
512
9
526
18
758
20
768
9
30 min
509
13
518
35
700
8
746
5
60 min
263
252
523
16
740
3
772
54
0.01% Ti0 2 ;
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
493
22
499
7
768
65
754
20
5 min
302
56
130
10
757
810
5
15 min
153
31
32
3
522
310
775
2
30 min
35
13
7
1
653
15
768
19
60 min
1
653
58
760
50
0.05% TiO,
Avg
Std Dev
Avg
Std Dev
17""
Avg
759
Std Dev
7
Avg
765
Std Dev
Omin
519
22
522
39
5 min
459
21
378
103
771
23
782
27
15 min
309
38
339
92
748
88
828
8
30 min
170
72
249
53
571
90
813
1
60 min
119
47
136
42
733
54
808
27
0.10% TiO,
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
562
11
458
1
774
11
767
86
5 min
539
57
496
1
792
23
764
52
15 min
471
34
424
8
770
9
750
59
30 min
410
17
358
13
674
4
768
48
60 min
327
30
315
1
750
10
756
65
109
Table 4-16
-continued.
-.-.-.-.-.-.-.-.-.-.-.-.-.•.-.-.-.■.-.-.-:-.%--.-;-.->.w.-.^
M4P-XYLENE
-.•.-.-.-.-.-.-.-.-.-.-.-.-.-.-.•.■.-.-.-.-.-.-.-
— — ■-."
UV Light pH 4
UV Light P H 7
Dark
pH4
Dark
pH7
0.00% TiO,
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
201
1
318
15
444
36
454
7
5min
204
6
287
47
514
38
498
22
15 min
217
7
308
53
466
2
511
18
30min
230
8
315
75
429
9
487
14
60 min
130
129
311
56
437
519
8
0.01% TiO.,
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
! 192
7
233
1
484
46
497
10
5 min
129
33
56
3
475
532
8
15 min
66
14
11
1
317
192
506
11
30 min
11
4
1
408
3
505
5
60 min
1
1
438
33
501
32
0.05% Ti0 2
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
206
13
246
10
497
3
534
29
5 min
194
2
186
44
495
12
542
18
15 min
126
29
168
36
495
49
575
4
30 min
68
36
114
14
341
62
559
3
60 min
47
23
65
20
459
44
556
1
0.10% TiO,
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
233
3
204
7
495
9
529
66
5 min
220
25
221
1
518
9
537
40
15 min
191
18
196
4
498
15
533
36
30 min
161
9
157
7
414
15
543
54
60 min
125
16
136
1
467
536
34
wX^-x*x-x-x-x-x-x-x-x-x-:-:-x-:-
■■»■■■ »■»■■■■..«
■»-■■» »"><»>
O-XYLENE
iMHWOMMMt x ■:-:■:■:-:-:■:• :
^,:, K ,,:.,:,:,
■*■—■»
.„.,.,...,.........,....„...,...„.„.,..
UV Light pH 4
UV Light
Dark pH 4
Dark
pH7
0.00% Ti0 2
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
52
1
107
5
145
20
147
4
5 min
54
3
86
24
178
18
165
12
15 min
60
1
97
27
157
1
169
8
30 min
67
4
100
35
142
3
164
2
60 min
40
39
98
29
148
2
178
5
0.01% Ti0 2
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
49
2
62
3
166
18
164
6
5 min
45
12
11
172
181
2
15 min
18
4
1
106
79
174
3
30 min
1
1
153
10
171
2
60 min
1
1
1
161
1
169
13
0.05% TiO, :
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
51
8
66
6
170
2
181
12
5 min
53
9
53
6
174
6
186
6
15 min
29
24
48
2
175
17
197
4
30 min
17
16
27
9
119
17
191
2
60 min
9
8
25
2
159
17
191
1
0.10% TiO, 1
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Avg
Std Dev
Omin
60
1
52
3
170
2
177
27
5 min
57
9
58
1
175
5
184
18
15 min
43
6
47
2
173
4
180
17
30 min
33
3
31
1
145
186
19
60 min
16
6
23
164
2
183
18
l ..... B . M .. WWM .„,„.,J
WMHMMMOMCMMWMM
BflMMMMaWMttMOCOOft
:*x.>x-:w>:*%v-x-:v.:-:.x-x-'-x
•X-X-X-X*X.Xs-X-X-X^*X*XXvO:-X-X-X-X-X-X.X-X<vW
110
o
c
I
20 40
Time (minutes)
60
Reactor 3 — ■— Reactor 4
Figure 4-31. Destruction of Benzene in Reactors 3 and 4 as a Function of
Time; Reactors Contained 0.01% Ti0 2 and were Irradiated for
60 minutes under UV Lamps (29 W/m 2 )
o
(a)
Ti0 2 Cone.
Control
0.01%
0.05%
0.10%
20 40
Time (minutes)
TiOj Cone.
Control
.01%
.05%
.10%
(b)
20 40
Time (minutes)
Figure 4-32. Benzene Concentration in UV Light (29 W/m 2 ) as a Function
of Time and Ti0 2 Concentration; Error Bars are One Standard
Deviation, (a) pH =4, (b) pH = 7
Ill
600
Ti0 2 Cone.
» Control
-0—0.01%
-fc-0.05%
-K-0.10%
(a)
20 40
Time (minutes)
Ti0 2 Cone.
Control
-0.01%
-0.05%
-0.10%
(b)
20 40
Time (minutes)
Figure 4-33. Toluene Concentration in UV Light (29 W/m 2 ) as a Function of
Time and Ti0 2 Concentration; Error Bars are One Standard
Deviation, (a) pH =4, (b) pH = 7
Initial observation of both the disinfection and detoxification data for
Ti0 2 photocatalysis suggested that the process displayed some efficacy.
Therefore, these data were selected for additional analysis by ANOM. For
disinfection the fractional survival of colony forming units after 120
minutes were selected. The normalized concentrations of benzene and
toluene after 30 and 60 minutes were used for the detoxification ANOM. An
a-level of 0.05 was selected for all of the data presented.
112
(a)
20 40
Time (minutes)
Ti0 2 Cone.
—&- Control
-o-0.01%
-A-0.05%
-tt-0.10%
(b)
- 400
n
S 350 _
§ 300
sLT^,
5 250; -J J-
200
e
150 4
a
| 100
X 50
4
1 o
20 40
Time (minutes)
Ti0 2 Cone
—$- Control
-a— 0.01%
-A-0.05%
-X-0.10%
Figure 4-34. m&p Xylene Concentration in UV Light (29 W/m 2 ) as a
Function of Time and Ti0 2 Concentration; Error Bars are One
Standard Deviation, (a) pH =4, (b) pH = 7
Data Analysis bv ANOM
ANOM was used to examine the controlled parameters for the
experiments, presence or absence of TJV light, pH level and Ti0 2
concentration. Based upon the ANOM, the presence and absence of light
and the concentration of both were deemed significant factors for both
disinfection and detoxification.
The grand average calculated for bacteria, as fractional survival,
was 0.66 (±0.20). The grand averages calculated for benzene were 0.75
113
(±0.05) and 0.70 (±0.08) for 30 and 60 minutes, respectively. The respective
values for toluene for 30 and 60 minutes were 0.76 (± 0.06) and 0.71 (±0.08).
The general values calculated for use in ANOM are given in Table 4-17.
Table 4-17. Calculated ANOM Values for Ti0 2 Photocatalysis
Grand Average, X
Avg Std Dev
Avg Range
Estimated
SD(X)
Bacteria @ t-120 min
0.66
0.20
0.40
0.28
Benzene @ t= 30 min
0.75
0.05
0.09
0.04
Benzene @ t= 60 min
0.70
0.08
0.15
0.09
Toluene @ t=30 min
0.76
0.06
0.11
0.05
Toluene @t=60 min
0.71
0.08
0.17
0.10
Effect of Lipht
UV light was measured in the lab experiments to be approximately
29 W/m 2 , a value slightly less than the measured values of UV light
available on a clear day. Therefore, the data gathered in the laboratory
experiments under UV light can be extrapolated to sunlight. Patel (1993)
and Wei et al. (1994) reported disinfection efficacy in sunlight to be greater
than in UV light.
The data from each of the sample sets were separated into two
subgroups based upon the absence and presence of light. This gave an n
value of 16 samples per subgroup and a k value of 2 subgroups for each
sample set. The n and k values were used to determine the degrees of
freedom, v, bias correction factor, d 2 \ and, subsequently, the ANOM critical
value, H, from the bias correction factor and critical values tables (Wheeler
1990). The corresponding values were v = 22.5, d,* = 3.571, and, for an a =
114
0.05, H = 1.47. These values, along with the values in Table 4-17, were used
to determine the decision limits using Equations 4-4 to 4-6.
For each subgroup, in this case UV light and dark, an average was
calculated and plotted on a chart with the decision limits. The subgroup
averages are shown in Table 4-18. As noted previously, a subgroup average
outside of the decision limits indicated a parameter was statistically
significant. As shown below the absence or presence of light was found to
be statistically significant for both disinfection and detoxification.
Table 4-18. UV Light Subgroup Averages for Ti0 2 Photocatalysis. Values
are Fractional Survival of Bacteria and Normalized Chemical
Concentration.
Subgroup
UV
'Light "(&W3fi
„_„„:::,.
->x->r-:-:-:v-x-:-:-:-:-:-:-:-:->:-:-:-:-:-:->
Dark
— "— —
X
s
R
X
S
R
Bacteria @ t=120 min
0.36
0.12
0.24
0.96
0.28
0.57
Benzene @ t = 30 min
0.55
0.05
0.09
0.95
0.05
0.10
Benzene @ t = 60 min
0.41
0.09
0.19
0.99
0.06
0.12
Toluene @ t= 30 min
0.57
0.05
0.10
0.95
0.06
0.13
Toluene @ t= 60 min
0.42
0.09
0.09
0.99
0.07
0.15
As demonstrated by the ANOM chart (Figure 4-35), the presence of
UV light had an appreciable impact on disinfection. This relationship is
shown graphically in Figure 4-38.
As shown in Table 4-15, there was some destruction of bacteria in the
presence of light and the absence of Ti0 2 , with N 24O /N values of 0.42 (±0.25)
and 0.77 (±0.03) for pH 4 and pH 7, respectively. This was not unexpected,
as the bactericidal effects of both UV light (Oliver and Carey 1976; Severin
et al. 1983; Wolfe 1990) and sunlight (Acra et al. 1990; Fujioka and
115
Narikawa 1982; Gameson and Saxon 1967) in aqueous systems have been
demonstrated.
Grand Avg
■0-3C--
UV Light
-UDLxbar
-LDLxbar Gavg » Light
Figure 4-35. Significance of UV Light (29 W/m 2 ), Based on ANOM, on
Bacteria in Ti0 2 Experiments at 120 Minutes
(a)
0.95
0.90
0.85
0.80
O 0.75
J 0.70
0.65
0.60
0.55
0.50
UDL = 0.77
- •Bark—
n,rand Avn
/
LDL = 0.73
♦ UV Light
-UDLxbar
-LDLxbar Gavg ♦ Light
(b)
1.00
0.90
0.80
J 0.70
O 0.60
0.50
0.40
0.30
-
• Dark
UDL = 0.77
1 ' ' / <jiaiiu nvy
T
trrr
LDL = 0.66
/
♦ UV Light
-UDLxbar'
-LDLxbar Gavg
"Light
Figure 4-36. Significance of UV Light (29 W/m 2 ), Based on ANOM, on
Benzene in Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes
116
1.00
0.95
0.90
0.85
= 0.80
§0.75
" 0.70
0.65
0.60
0.55
0.50
UDL = 0.78
• Dark
_ ' " —
trro
.. LDL = 0.73
• UV Light
-UDLxbar ■
-LDLxbar Gavg — •— Light
1.00
0.90
0.80
cj0.70
a o.6o
0.50
0.40
0.30
UDL = 0.77
f Dark —
trn
LDL = 0.66
# UV Light
-UDLxbar
-LDLxbar Gavg
Figure 4-37. Significance of UV Light (29 W/m 2 ), Based on ANOM, on
Toluene in Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes
0.70
>t=2 hrs
lt=4 hrs
UV Light
Dark
Figure 4-38. Effect of UV Light (29 W/m 2 ) on Fractional Survival of Bacteria
in All Reactors in Ti0 2 Experiments; Bars are One Standard
Deviation
117
Effect of pH
As was done for evaluation of the effect of sunlight the data from each
sample set were separated into two subgroups, based upon the pH value of 7
or 10. Since k and n were the same, and the same a-level was used, the
values for v, d 2 * , and H were also the same. Again these values, along with
the values in Table 4-17, were used to determine the decision limits using
Equations 4-4 to 4-6.
For each subgroup, in this case pH = 4 and pH = 7, an average was
calculated and plotted on a chart with the decision limits. The subgroup
averages for pH are shown in Table 4-19 and the ANOM charts are shown
in Figures 4-39 to 4-41.
Table 4-19. pH Subgroup Averages for Ti0 2 Photocatalysis. Values are
Fractional Survival of Bacteria and Normalized Chemical Concentration
Subgroup
pH = 4
pH = 7
X
S
R
X
s
R
Bacteria @ t=
=120 min
0.61
0.17
0.35
0.71
0.23
0.46
Benzene @ t=
=30
min
0.69
0.06
0.11
0.80
0.04
0.08
Benzene @ t=
=60
min
0.63
0.11
0.22
0.77
0.05
0.09
Toluene @ t=
:30
min
0.70
0.06
0.13
0.82
0.05
0.10
Toluene @ t=
:60
min
0.65
0.12
0.24
0.78
0.04
0.09
iMMMMMHMtt
.-.-.-.-.-.-.-.-.-.-.-.-.-.-.■.-.-.-.•.■.-.■.-.-.■.-.-.■.
lOOMMMMMMWHMC
w.\^w.w.w.-.w.-.w.w.w.w.
MMMMMMMMMMOM
-.-.-.-.-.-.-.-.■.•.■.■.-.-.-.-.-.-.-.-.-.-.-.-.-.-.•.-.-.
■.-.-.-.-.-.-.-:-.-.-.-.-:-.-.-.-:-.-:-.-.-:-.-.-:v.-.-.-
118
0.80
0.75 ■
0.70
1 0.65 -
0.60 -
0.55
0.50
UDL = 0.77
>pH = 7
/ Grand Avg
^pH = 4
LDL = 0.73
■ r^i i ^
Figure 4-39. Significance of pH, Based on ANOM, to Bacteria Destruction in
Ti0 2 Experiments at 120 Minutes
ANOM demonstrated that, at the levels tested, pH had no significant
effect on the destruction rate of the mixed bacteria species, E. coli,
Pseudomonas aeruginosa, and Serratia marcescens. These findings are
consistent with the findings of Block et al. (1997), who studied the effect of
pH on the inactivation of Serratia marcescens and reported that acidic and
neutral pH values, from 3.5 - 7, had no perceptible impact on disinfection
efficacy.
Examination of the charts above suggested that ANOM tests were
somewhat inconclusive for detoxification. The data suggested that pH
could be statistically significant; however, the proximity of subgroup
averages, particularly at 60 minutes, to the decision limits indicated a need
for caution. With an a-level of 0.05 values close to the decision limits were
possibly false signals.
The acid pH of 4 appeared to be slightly more effective than the
neutral pH of 7. As shown above there was a slight difference between the
mean normalized concentrations of BTEX components after 30 minutes and
119
60 minutes. While the significance of this was not conclusive, the data
were consistent with values reported by (Kawaguchi and Furuya 1990), who
found that 3.5 was an optimum pH for the Ti0 2 photocatalyzed degradation
of chlorobenzene.
(a)
0.85
0.80
0.75
J 0.70
o 0.65 ■-
0.60
0.55
0.50
— U ---I 7 ^zzzz 7 —9i°£**j.
■UDLxbar'
-LDLxbar Gavg — ■ 4 — Light
0.80
0.75
0.70
^0.65
c3
0.60
0.55
0.50
UDL = 0.75
^pH = 7
/ Grand Avg
r
XTA3
LDL = 0.65
^pH = 4
■UDLxbar ■
■LDLxbar Gavg » Light
(b)
Figure 4-40. Significance of pH, Based on ANOM, to Benzene Destruction
in Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes
The concentration of Ti0 2 appeared to have a significant impact on
disinfection. In order to clarify the meaning of the differences seen with
Ti0 2 concentration, ANOM tests were performed for bacteria at 120
minutes, and benzene and toluene at 30 and 60 minutes. The data were
divided into four subgroups based upon the concentration of Ti0 2 . This gave
an n value of 8 samples per subgroup and a k value of 4 subgroups for each
120
sample set. The n and k values were used to determine v, d/, and H from
the appropriate tables (Wheeler 1990). The corresponding values were v =
24.4, d/ = 2.876, and, for an a = 0.05, H= 2.29. These values, along with the
values from Table 4-17, were used to determine the decision limits using
Equations 4-4 to 4-6.
(a)
0.85
0.80
0.75
O 070
O 0.65 -■
0.60
0.55
0.50
UDL = 0.78 >PH = 7
LDL = 0.73 ^h = 4
Gro n d Av g
TT7S-
■UDLxbaf
■LDLxbar Gavg ♦ Light
o
O
0.80
0.75
0.70
0.65
0.60
0.55
0.50
UDL = 0.77
#PH = 7
/ Grand Avg
I
urrr T
LDL = 0.66
• pH = 4
-UDLxbar-
-LDLxbar Gavg ♦ Light
(b)
Figure 4-41. Significance of pH, Based on ANOM, to Toluene Destruction in
Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes
Effect of TiO o Concentration
For each subgroup an average was calculated and plotted on a chart
with the decision limits. The calculated subgroup averages are shown in
Table 4-20 and the ANOM charts are shown in Figures 4-42 to 4-44.
121
Table 4-20. Ti0 2 Concentration Subgroup Averages for Disinfection. Values
are Fractional Survival of Bacteria and Normalized Chemical
Concentration
Subgroup
Control 0.01% TiO ?
X s R X s R
0.05% Ti0 9
0.10% TiO,
R
R
Bacteria @
t=120 min
Benzene @
t=30 min
Benzene @
t=60 min
Toluene @
t=30 min
Toluene @
t=60 min
0.93 0.10 0.21 0.48 0.11 0.23 0.36 0.09 0.18 0.71 0.44 0.89
0.99 0.04 0.07 0.49 0.03 0.06 0.57 0.11 0.22 0.86 0.03 0.06
0.89 0.16 0.31 0.48 0.06 0.12 0.45 0.07 0.14 0.83 0.03 0.06
1.05 0.05 0.10 0.49 0.04 0.59 0.04 0.08 0.59 0.10 0.85 0.10
0.09 0.17 0.33 0.45 0.06 0.12 0.45 0.09 0.17 0.81 0.02 0.05
1.00
0.90
0.80
0.70
o 0.60
>0.50
2 0.40
0.30
0.20
0.10
0.00
UDL = 0.89 n No TiO
LDL = 0.43
0.10% Grand Ave
TJ.6B -
0.05%
-UDLxbar
Gavg
-LDLxbar
-Ti02 Cone
Figure 4-42. Significance of Ti0 2 Concentration, Based on ANOM, on
Bacteria in Photocatalysis Experiments at 120 Minutes
Since Ti0 2 concentration displayed some significance for both
disinfection and detoxification, the subgroup averages were plotted against
the control and the two concentrations which were closest together against
each other to determine the minimum significant concentration. These
combinations allowed for the determination of the optimum concentration
range for the fastest destruction. There were again two subgroups, for a k
of 2, with the n value (samples per subgroup) remaining at 8. The
corresponding table values were v = 17.8, d 2 * = 3.304, and, for an a = 0.05, H
= 1.54.
(a)
1 nr\
P No Ti0 2
0.90
\
0.80
UDL = oW P0.10%
_\ / Grand Avg
O
"ft 0.70 -
o
\ / ° /b
LDL = 0.7o\ /
0.60 -
\ JlO.05%
0.50
cr{foi%
n An
Gavg — — Ti02 Cone
(b)
0.90
0.85
0.80
0.75
o 0.70
O
~S 0.65
0.60
0.55
0.50
0.45
0.40
"No Ti0 2
UDL =
LDL = 0.60
0.10%
Grand Avg
■-TJ.70 - *
0.05%
■UDLxbar
Gavg
■LDLxbar
-Ti02 Cone
Figure 4-43. Significance of Ti0 2 Concentration, Based on ANOM, on
Benzene in Photocatalysis Experiments; (a) 30 Minutes (b) 60
Minutes
(a)
(b)
123
1.10
1.00
0.90
(3 0.80
O 0.70
0.60
0.50 ■■
0.40
No TiO
UDL
LDL = 0.7
0.10%
GrancTEvc
-y tr.7B -
-UDLxbar
Gavg
-LDLxbar
-Ti02 Cone
1.00
0.90
0.80
o
o
"S 0.70
o
0.60
0.50
0.40
UDL =
No TiOz
).83
LDL = 0.59
1 0%
Grand Ave
— TJ.7T
0.05%
-UDLxbar
Gavg
-LDLxbar
-Ti02 Cone
Figure 4-44. Significance of Ti0 2 Concentration, Based on ANOM, on
Toluene in Photocatalysis Experiments; (a) 30 Minutes (b) 60
Minutes
Examination of the ANOM charts (Figures 4-45 to 4-52) indicated that
while there was no significant difference between 0.01% Ti0 2 and 0.05%
Ti0 2 for either disinfection or detoxification, both concentrations were
more effective than 0.10% and no Ti0 2 . This was consistent with the initial
trends observed wherein 0.01% was observed to be the most effective
concentration.
124
1 nn
0.90 -
0.80
o
% 0.70 -
Z
0.60
0.50
n 4fi
q No Ti0 2
UDL = 0.86 \
\ Grand Ave
LDL = 0.55 \
□ 0.01%
Gavg — D — Ti02 Cone
Figure 4-45. Comparison of Control vs. 0.01% Ti0 2 on Photocatalytic
Disinfection at 120 Minutes, Based on ANOM
1.00
0.90
0.80
o
1*0.70
0.60
0.50 4
0.40
UDL = 0.88
Q No Ti0 2
Grand Ave
LDL = 0.57
D 0.05%
-UDLxbar
Gavg
■LDLxbar
-Ti02 Cone
Figure 4-46. Comparison of Control vs. 0.05% Ti0 2 on Photocatalytic
Disinfection at 120 Minutes, Based on ANOM
125
1.00
0.95
0.90 4
O 0.85
% 0.80
Z 0.75
0.70
0.65
0.60
UDL = 0.97
Grand Ave
D0.10%
0.82
LDL = 0.67
■UDLxbar
Gavg
-LDLxbar
-Ti02 Cone
Figure 4-47. Comparison of Control vs. 0.10% Ti0 2 on Photocatalytic
Disinfection at 120 Minutes, Based on ANOM
n 70
UDL = 0.65
0.60
0.50
wnn# JUB *- -Tm- q
£ 0.40
2 0.30
' LDL = 0.35
0.20
0.10
O 00
■- uuLXDar LULxoar
Gavg — □ — Ti02 Cone
Figure 4-48. Comparison of 0.01% vs. 0.05% Ti0 2 on Photocatalytic
Disinfection at 120 Minutes, Based on ANOM
126
n on
Q No Ti0 2
0.80
0.70
0.60
O 0.50 -
O 0.40 -
UDL = 0.76 \
V
Grand Ave
TJ.58 - "
LDL = 0.61 \
D0.01%
0.30
0.20
0.10
n nn -
-LDLxbar
Gavg — D —
-Ti02 Cone
Figure 4-49. Comparison of Control vs. 0.01% Ti0 2 on Photocatalytic
Destruction of Benzene at 60 Minutes, Based on ANOM
1.00
0.90
0.80
0.70
o 0.60
O
~&0.50
°0.40
0.30 4
0.20
o.io 4
0.00
UDL = 0.83
No Ti0 2
LDL = 0.68
urana Ave
■""rj.75 - *
0.05%
■UDLxbar
Gavg
■LDLxbar
-Ti02 Cone
Figure 4-50. Comparison of Control vs. 0.05% Ti0 2 on Photocatalytic
Destruction of Benzene at 60 Minutes, Based on ANOM
127
1.00
0.95
0.90
(3 0.85
O 0.80
075
0.70 4
0.65
.. UDL = 0.93
UNo Ti0 2
XI 0.10%
Grand Ave
TT.56-"
LDL = 0.79
-UDLxbar
Gavg
-LDLxbar
-Ti02 Cone
Figure 4-51. Comparison of Control vs. 0.10% Ti0 2 on Photocatalytic
Destruction of Benzene at 60 Minutes, Based on ANOM
0.70
0.60
O 0.50
8
O
0.40
030
0.20
UDL = 0.62
0.05%
-/—
Grand Av(
■0■.■5~4- ,
LDL = 0.47
0.01%
•UDLxbar
Gavg
-LDLxbar
-Ti02 Cone
Figure 4-52. Comparison of 0.01% vs. 0.05% Ti0 2 on Photocatalytic
Destruction of Benzene at 60 Minutes, Based on ANOM
The disinfection results of this study were compared with those
reported by Patel (1993), Block et al. (1997) and Wei et al. (1994). The latter
two studies both reported that a concentration of 0.01% Ti0 2 was optimum
for destruction of Serratia marcescens and Escherichia coli. Patel found
that consistent inactivation of Serratia marcescens and Pseudomonas
aeruginosa, both in sunlight and UV light, was achieved with a Ti0 2
concentration of 0.01%.
128
The superior effectiveness of 0.01% and 0.05% Ti0 2 over 0.10% Ti0 2
concentrations for detoxification of BTEX was not anticipated, as others
have found 0. 10% Ti0 2 to be the optimum concentration for the destruction
of BTEX (Goswami et ai. 1993; Oberg 1993). It is conceivable that the
presence of bacteria had some influence on light penetration, such that
light penetration at the higher levels of Ti0 2 was not as strong.
Experiments would need to be designed to consider the effect of the turbidity
of the water in order to prove this.
Multiple Parameter Effects
Evaluation of the effects of multiple parameters helped to clarify the
role played by each (Ti0 2 , UV light and pH) on the destruction of the tested
components. When all parameters were considered together, it appeared
that the most effective treatment for both disinfection (Table 4-21) and
detoxification (Table 4-22) consisted of photocatalysis with 0.01% Ti0 2 at a
pH of 4. Figures 4-53 and 4-54 show the effects of light and pH together on
fractional survival of bacteria and the destruction of benzene. As was
shown by the ANOM, however, the impact of the pH was not significant,
and the 0.01% and 0.05% Ti0 2 concentrations do not produce significantly
different effects.
Table 4-21. Mean Values for Fractional Survival as a Function of Light, pH
and Ti0 2 Concentration at t=240 Minutes
fi0 2 Concentration Light pH 4 Light pH 7 DarkpH4 DarkpHf
0.00% 0.63 089 i'.2l"" L01
0.01% 0.00 0.08 0.87 0.96
0.05% 0.02 0.10 0.75 1.19
0.10% 0.16 0.05 0.89 1.10
129
Table 4-22. Mean Normalized Benzene Concentration After 30 Minutes in
Ti0 2 Experiments
TiO> Concentration
Light pH 4
Light pH 7
Dark pH 4
Dark pi
0.00%
1.01
0.98
0.90
1.07
0.01%
0.08
0.02
0.85
1.01
0.05%
0.31
0.47
0.80
1.05
0.10% 0.74
0.79
.■.v.-.-..-.-.--.-.-.-.-.-.-.-.-.-.-.-.-.\-.-.-.-.-.-.-.-.v.-.-.-.-.
0.86 1.04
\v;v;"/; , ; , ; , ;v.v.-.v.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-. ■.-.■.■.■.■.■.-,-.-.■.■.■.-
Effect of Initial Colony Density on Disinfection
The large range (1177 x 10 :i cfu/L) and average standard deviation
(67%) of the initial bacterial colony density (Table 4-23) required the
exploration of its impact on disinfection. No linear or logarithmic
relationship was found for initial bacterial colony density with fractional
survival. A linear regression analysis of initial colony density with N l20 /N
yielded an r 2 of 0.02, at a 95% confidence level and a p-value of 0.36. For
ln(N 120 /N ) as a function of initial colony density, least squares linear
regression at a 95% confidence level yielded an r 2 of 0.01, with a p-value of
0.22.
No trend was discernible by graphical examination of the data either.
Figure 4-55 shows the relationship between initial colony density and
N 30 /N , using data from individual reactors. The finding of no correlation
of fractional survival rates with initial colony density was in accord with
results reported by Li et al. (1996), who compared the destruction of E. coli
for two different initial coliform densities, 400/L and 110/L, and found only a
slightly higher destruction rate with the lower initial density, and no
difference after one hour.
130
1.80
1.60
1.40
1.20
z 100
z 0.80
0.60
0.40
0.20
0.00
1 22
119 1.08 L
0.89
0.20
0.28
-,-0.18
0.10
uv
Light
(4)
UV
Light
(7)
Dark
(4)
Dark
(7)
Qt=2 hrs
Bt=4 hrs
Figure 4-53. Fractional Survival of Bacteria as a Function of UV Light (29
W/m 2 ) and pH in Ti0 2 Experiments; Bars are One Standard
Deviation
1.40
1.20
1.00 -
^ 0.80
0.94 1-04V 05
0.89
130 minutes
i60 minutes
Dark
pH7
Figure 4-54. Effect of UV Light (29 W/m 2 ) and pH on the Destruction of
Benzene in Ti0 2 Experiments; Bars are One Standard Deviation
Table 4-23. Descriptive Statistics for Initial Colony Density in Ti0 2
Experiments
Parameter
Initial Bacteria Density, cfu JL x 10 4
Mean
335
StdDev
226
Min
67
Max
.^^•.^^.V>.v>>>;v.■.^■.■.■.■.•.-.-.•.-.•.•.■.-.■.^■.^-.■.-.-.-.•.•.•
1244
.^v.v.-.v.-.^-.v.w.-.-.vAsv.-.-.v.-.-:-.v.-.%\^^^
131
Other Effects
There were two other effects which merited mention, although the
experiments were not designed to account for them specifically. Both the
presence of multiple bacteria species and the combination of bacteria and
VOCs were likely to have had some impact on both disinfection and
detoxification.
9 nn
1.80
, *
1.60
1.40
.♦•
. 1.20 -
1 1.00
2 0.80
0.60
0.40 -
•*b * * ♦
0.20
0.00
***U / •
•^^^«» •
500 1 000
1500
Initial Colony Density, cfu x 10 3 /L
Figure 4-55. Initial Colony Count vs. Fractional Survival of Bacteria at t=120
Minutes for Ti0 2 Photocatalysis
Interaction between the bacteria and the VOCs was very likely as the
BTEX could serve as a substrate for the bacteria, causing the organisms to
multiply. Specifically, P. aeruginosa has been used successfully to degrade
pentachlorophenol (Premalatha and Suseela Rajakumar 1994).
Previous photocatalytic disinfection work (Block et al. 1997; Ireland
et al. 1993; Patel 1993; Wei et al. 1994) examined the destruction of
individual bacteria species. The longer reaction times experienced in this
study could be a function of the presence of multiple bacteria species.
132
However, as the experiments were not designed to discern this, additional
work would need to be done in order to confirm this.
Photocatalvsis vs. Air Stripp in g
The chemical contaminants (BTEX) are very volatile and therefore
subject to air stripping (The system tested in these experiments, Ti02
photocatalysis, yielded positive results at all conditions tested.
Consequently, the process shows promise for application in small
communities. However, as evidenced by the efficacy of the
photosensitization process for the destruction of bromacil, coupled with its
ineffectiveness for the destruction of benzene and toluene, it is critical that
any system be tested for the specific contaminants of a water source.
Table 4-24). In order to determine how much, if any, of the BTEX
reduction was due to air stripping, dark control experiments were
conducted. As shown in Figures 4-56 and 4-57, there was essentially no
reduction observed in any of the BTEX components during the dark
experiments with Ti0 2 at either pH value. The apparent decrease at 15
minutes for pH 4 (Figure 4-57) was within the standard deviation of 16%
and evidence of error encountered in sampling and analysis. The
precautions taken to limit air stripping, minimal headspace and parafilm
sealing of the reactor, were sufficient to alleviate transfer of the chemical
contaminants to the atmosphere. The results reported herein were
consistent with results reported from outdoor pilot scale experiments
conducted by (Oberg 1993) and Madabhushi (1997). Both reported less than
10% reduction in dark tests. Oberg did report on one dark test which
resulted in an 80-85% reduction of all BTEX components, however, the test
133
was conducted with a large air space above the water, wherein a 380 liter
tank was filled with only 57 liters of water.
The system tested in these experiments, Ti0 2 photocatalysis, yielded
positive results at all conditions tested. Consequently, the process shows
promise for application in small communities. However, as evidenced by
the efficacy of the photosensitization process for the destruction of bromacil,
coupled with its ineffectiveness for the destruction of benzene and toluene, it
is critical that any system be tested for the specific contaminants of a water
source.
Table 4-24. Vapor Pressure Values for BTEX components.
Component
Vapor Pressure © 25 °C (mm Hg)
Boiling Point @ 1 atm
Benzene
94
80.1
Toluene
28.9
110.8
o-Xylene
6.4
144
m-Xylene
8
139.3
p -Xylene
8.6
HWOOWWOWOWWWMtOW
_„„,.,
,,,:,,,,,,
138.5
:-:-:->>x-::::-:-;-;;<;:-x-:v:::::-:->:;:<::;::-:-k->>>:-:-:-:<-:v:-^
20 40
Time (minules)
Benzene
Toluene
m&p-Xylene
-o-Xylene
Figure 4-56. Normalized Concentrations of BTEX Components in pH 7 Dark
Experiments with 0.01% Ti0 2
134
20 40
Time (minutes)
Benzene
Toluene
mAp-Xylene
o-Xylene
Figure 4-57. Normalized Concentrations of BTEX Components in pH 4 Dark
Experiments with 0.01% Ti0 2
Summary
Examination of the conditions under which Ti0 2 photocatalysis was
most effective brings up two aspects for consideration. On the positive side,
pH was not a significant factor and no pH adjustments would be required.
The specificity of the concentration of Ti0 2 , however, is a disadvantage for
the applications considered here. The dosage of Ti0 2 must be fairly tightly
controlled as too much could result in inhibition of the photocatalytic
reaction. However, the low Ti0 2 dosage requirements do offer an advantage
in that operational costs are minimized.
In order for this process to be determined feasible for application,
two areas of research should be addressed. First, the issue of
immobilization or separation of the catalyst and associated cost, must be
examined. This may be accomplished via the use of a small filter, however,
such a system should be tested. Secondly, the system must be tested over a
much broader range of microbiological and chemical contaminants,
135
including viruses. Site specific testing is a must, as microbiological species
may differ from one locale to the other.
TiO „ Photocatalvsis Combined With Methylene Blue
Several experiments were conducted using both Ti0 2 and MB. These
combination experiments were conducted in order to determine if the use of
a dye in combination with Ti0 2 would enhance the photochemical process
by extending the range of photons available for photochemical reaction.
In order to ensure reproducibility of the results, each set of
experiments was conducted three times. Four reactors were run at a time,
each reactor containing either no photochemical, 0.01% Ti0 2 , 5 mg/L MB,
or a combination of 0.01% Ti0 2 and 5 mg/L MB. A complete set of
experiments was defined as two groups of four reactors, one group in
sunlight and one group in the dark.
Samples were taken from each reactor at time intervals of 0, 5, 15, 30,
60, 120 minutes and refrigerated immediately. Three replicates from each
sample were plated for microbiological analysis. The remainder of the 0, 30
and 120 minute samples was refrigerated and saved for chemical analysis.
For the experiments conducted in sunlight, both the total insolation
and the UV light intensity were measured and recorded over the duration
of the experiment. Total insolation ranged from 433 W/m 2 to 853 W/m 2 , and
the total UV intensity measurements ranged from 25 to 40 W/m 2 . The
recorder was jammed for approximately the last half hour of the set three
experiment. Values for that portion of the experiment were estimated
based on measurements before the recorder jammed and the maximum
136
and minimum values during this time period (as determined by the high
and low of the pen marks). The average total insolation measured in each
experiment is given in Table 4-25, and graphs of the total insolation are
shown in Appendix B.
Table 4-25. Measured Sunlight Intensity in Combination Experiments
Set ^ Total Avg Insolation, W/n?" Total ''Avg 'UV,' Win 1
#2 853 40
#3 433 25
General Comments About Experimental Data
The average standard deviation of the disinfection data was 13%.
Plates on which the colonies were not individually identifiable and those
with severe contamination were not counted, which resulted in the loss of
11-37% of the 144 plates in a given experimental set.
The average standard deviations of the detoxification data were much
higher than in either of the other experimental groups, 23% for benzene
and 56% for toluene. However, when normalized concentrations were
used, the average standard deviation was lower, 14% for benzene and 17%
for toluene, although they still exceeded the values of the other two
experimental groups. The average standard deviation values are given in
Table 4-26.
Sample loss for detoxification occurred when the sample was
dropped and broken prior to analysis, which occurred once in experimental
set number one. The dropped sample was an initial sample, 43 , and the 5
137
minute sample was substituted. Chemical samples were generally
analyzed within two weeks of the experiment.
Table 4-26. Average Standard Deviations for all Combination Experiments
Benzene (ppb)
-:-X-X%-:%<%%<oC-X-x-:-:-:-:-:-:o:o*:->x<^
StdDev Avg
Toluene (ppb)
" StdDev Avg'
E.Coli (cfuxltfVL
StdDev Avg
Raw Data 120 511
Normalized Data 0.11 0.77
199 357
0.12 0.72
119 651
0.13 0.50
Statistical Treatment of the Data
The data were treated as outlined in the section on dye
photosensitization. No specific adjustments were required for the data,
with the exception of normalizing negative percentages of destruction to
zero. No outliers were observed.
Disinfection
Since both MB and Ti0 2 increased the efficiency of disinfection of E.
coli bacteria over sunlight or UV light alone, it was anticipated that the
combination would be better than either alone. However, as shown in
Figure 4-58, there was little difference between using Ti0 2 alone, MB alone
or a combination of Ti0 2 and MB. The use of a photochemical, however, did
improve disinfection over sunlight alone (Table 4-27). In the presence of
MB, either with or without Ti0 2 there was a 95% coliform reduction within
5 minutes and complete disinfection within 15 minutes. A coliform
reduction of 95% was reached by 15 minutes with Ti0 2 and not until GO
minutes in sunlight alone. Total disinfection was not observed until the 30
minute samples with Ti0 2 and 120 minutes in sunlight alone.
138
The data were analyzed by ANOM (as outlined previously) to
determine the effect of sunlight and photochemicals on disinfection. The
fractional survival at 5, 15 and 30 minutes were analyzed in this manner.
The grand average values for E. coli destruction at 5, 15 and 30 minutes
were 0.63 (±0.16), 0.57 (±0.14), 0.52 (±0.12), respectively. The general values
for the ANOM are shown in Table 4-27.
For determination of the effect of sunlight, the sample sets were
divided into two subgroups (k=2) with twelve observations per subgroup
(n=12). The corresponding table values were v = 17.8, d,* = 3.304, and, for a =
0.05, H = 1.49. These values, along with the values in Table 4-28, were used
to determine the decision limits using Equations 4-4 to 4-6. The calculated
subgroup averages, shown in Table 4-29, were then plotted on a chart with
the decision limits, and the significance of the presence of sunlight was
determined. As anticipated, the presence or absence of sunlight was a
statistically significant factor in all of the sample sets, as shown in Figure
4-59.
Avg S.D. = 16.9%
Control
— Q-
-Ti02
—br
MB
-X- Both
50 100
Time (minutes)
150
Figure 4-58. Destruction of E. coli in Sunlight 0,- A „ = 433-853 W/m 2 , 1,^ Avg
= 25-40 W/m 2 ) in Combination Experiments
139
Table 4-27. Mean Fractional Survival (±14.1%) of E. Coli in Combination
Experiments
Control Samples 61% TiOg
Sunlight Dark Sunlight Dark
' N5/N0' 1.10 1.21 0.62 0.61
N 15 /N 0.99 1.32 0.05 0.91
N 30 /N 0.63 1.30 0.00 0.82
N^/No 0.05 1.29 0.00 0.55
tWN 8 0.00 1.11 0.00 0.94
5mg/LMB 0.1% TiQ 3 & 5 mg/L MB
Sunlight Dark Sunlight Dark
N 5 /N 0.04 0.70 0.01 0/73
N 1S /N 0.00 0.66 0.00 0.64
N 30 /N 0.00 0.64 0.00 0.77
Ngo/No 0.00 0.36 0.00 0.61
N 120 /N„ 0.00 0.65 0.00 0.59
Table 4-28. Calculated ANOM Values for Combination Experiments
Sample Set
Grand Average, X
Avg Std
Dev
Avg Range
Estimated
SD(X)
E. coli @ t=5 minutes
E. coli @ t= 15 minutes
E. coli @ t=30 minutes
Benzene @ t= 30 minutes
Benzene @ t= 120 minutes
Toluene @ t= 30 minutes
Toluene @ 120 minutes
0.63
0.57
0.52
0.69
0.84
0.81
0.63
0.16
0.36
0.14
0.31
0.12
0.30
0.01
0.22
0.12
0.28
0.14
0.33
0.01
0.23
0.21
0.18
0.16
0.11
0.15
0.16
0.12
.v.v.-.w:*:v:-.-;-:^-:-.-:-:-.-:-.vv;
Table 4-29. Sunlight Subgroup Averages for Combined Experiments.
Values are Fractional Survival of Bacteria and Normalized Chemical
Concentration
Sunlight ( 433-853 W/m 2 )
Dark
X
S
R
X
S
R
E. coli @ t= 5 minutes
0.44
0.05
0.12
0.81
0.26
0.60
E. coli @ t=15 minutes
0.26
0.02
0.05
0.88
0.25
0.56
E. coli @ t= 30 minutes
0.16
0.06
0.15
0.88
0.19
0.45
Benzene @ t= 30 minutes
0.76
0.14
0.32
0.93
0.10
0.24
Benzene @ t= 120 minutes
0.55
0.08
0.18
0.83
0.11
0.26
Toluene @ t= 30 minutes
0.68
0.17
0.39
0.93
0.11
0.26
Toluene @ t= 120 minutes
0.48
0.05
140
In order to clarify the impact of the photochemicals on disinfection,
ANOM was performed. The data were divided into four subgroups based on
the photochemical used in the reactor. This gave an n value of 6 samples
per subgroup and a k value of 4 subgroups for each sample set. The
corresponding table values were v = 18.1, d 2 * = 2.569, and, for a = 0.05, H =
2.35. These values, along with the values in Table 4-28, were used to
determine the decision limits using Equations 4-4 to 4-6.
The calculated subgroup averages (Table 4-30) were plotted on a chart
with the decision limits, and the significance of photochemicals was
determined. The presence or absence of photochemical was a statistically
significant factor in all of the sample sets, as shown in Figure 4-60.
Table 4-30. Photochemical Subgroup Averages for Combination Experiments;
Values are Fractional Survival of E. coli and Normalized Chemical Concentration
■x<o>x-x->:-x%->>:<<<<<<'>>>x-:-:o:-x->x-:->>>>>:-:-:-:-'-'.:.r-:.x.::---
Control 0.01% TiO, 5 mg/L MB Both
xsRxsRx s Rx s R
Rcoii @t=5min 1.07 0.06 0.11 0!57 0.30 0.59 6.32 0.20 0.40 6.40 0.02 ftoT
E.coli @t=15min 1.08 0.03 0.05 0.55 0.07 0.14 0.30 0.20 0.38 0.28 0.16 0.32
E.coli @t=30min 0.81 0.11 0.22 0.42 0.10 0.20 0.30 0.12 0.24 0.38 0.10 0.19
Benzene @ t=30 min 0.89 0.08 0.16 0.83 0.21 0.42 0.97 0.06 0.11 0.75 0.14 0.29
Benzene @t=120min 0.81 0.14 0.28 0.50 0.08 0.15 0.86 0.09 0.18 0.65 0.12 0.24
Toluene @t=30 min 0.85 0.11 0.22 0.77 0.18 0.35 0.92 0.04 0.08 0.69 0.20 0.39
Toluene @ t=120 min 0.77 0.12 0.25 0.44 0.05 0.10 0.74 0.16 0.32 0.55 0.10 0.20
In order to discern if there was any differentiation in the treatments,
the different photochemical subgroup averages were plotted against each
other. The new decision limits were based on a k of 2 and an n of 6, which
changed the table values to v = 9.2, d 2 * = 2.603, and, for a = 0.05, H = 1.6. The
plotted subgroup averages are shown in Figures 4-61 to 4-63.
141
(a)
90
0.80 -
-UDL = 0.72
XDark
0.70
0.60
Z> 0.50 -
z 0.40 -
/ Grand Avg
I
LDL = 0.54
XSun
ight
0.30 -
0.20
0.10 -
00
i mi v
-LDLx -■
(b)
0.90
0.80
0.70
0.60
Z 0.50
1
z 0.40
0.30
0.20
0.10
0.00
5 Dark
UDL = 0.65
J-
Grand Avg
D"57
LDL = 0.49
XSunlight
-UDLx
-LDLx Gavg
■Light
(O
0.90
0.80
0.70
0.60
Z 0.50
1 0.40
0.30
0.20
0.10
0.00
._
rDafx
UDL = 0.59
.=
J.
Cjrand Avg
0"52 '
LDL ■ 0.45
-
XSunlight
-UDLx
-LDLx Gavg — K — Light
Figure 4-59. Significance of Sunlight (L^ AvK = 433-853 W/m 2 , l m Ave = 25-40
UV, Avg
W/m ) on E. coli Destruction, Based on ANOM, in Combination
Experiments; (a) 5 Minutes (b) 15 Minutes (c) 30 Minutes
142
The ANOM demonstrated clearly what the graphical display of the
data suggested. There was no statistically significant difference between
the use of MB, Ti0 2 or a combination of the two in photochemical
disinfection.
Detoxification
The addition of MB to the Ti0 2 photocatalyzed reaction appeared to
have an inhibitory effect on detoxification. After 120 minutes in sunlight
(I T ot, Av g = 433-833 W/m 2 , I UVi Avg = 25-40 W/m 2 ), reactors dosed with 0.01% Ti0 2
showed a 94% reduction of benzene and a reduction of toluene below
detectable limits (Figure 4-64). However, when 0.01% Ti0 2 was combined
with 5 mg/L MB and exposed to the same intensity sunlight for 120
minutes, only a 65% and 70% reduction in benzene and toluene,
respectively, was observed. The mean concentrations of both benzene and
toluene in the combination experiments are shown in Table 4-31.
While the conclusions seemed to be clear, an ANOM was performed
to clarify the distinction between the use of Ti0 2 alone and the combination
of Ti0 2 and MB. The data were divided into four subgroups as outlined
above in the disinfection section, with the same values used for calculation
of decision limits, for both four subgroups and two subgroups. The
subgroup averages are shown in Table 4-30. Selected ANOM charts are
shown as Figures 4-65 to 4-68.
143
(a)
1.20
0.00
— UDLxbar
■-Gavg
Grand_Aya
~ 0.63
-LDLxbar
-Photochemical
(b)
1.20
1.00
0.80
o
"2 0.60
2
0.40
0.20
0.00
-UDL = 0.74
Q Control
Grand Avg_
Ti0 2 N.
0.57
LDL = 0.40
-fcW — DBoth
-UDLxbar
Gavg
-LDLxbar
-Photochemical
(0
0.90
0.80
0.70
0.60
:0.50
:0.40
0.30
0.20
0.10
0.00
D Control
.UDL = 0.67
\
\ Grand Avg_
_.
\ d u. ° 52
ViO, ?oth
LDL = 0.37
NhjT
-UDLxbar
Gavg
-LDLxbar
-Photochemical
Figure 4-60. Significance of Photochemical on E. coli Destruction, Based on
ANOM, in Combination Experiments; (a) 5 Minutes (b) 15
Minutes (c) 30 Minutes
144
(a)
u.ou
0.70
UDL = 0.63
0.60 -
0.50 ■
Ti0 2 °Sw
Grand Avg_
0.40 ■
\n MB
049
0.30 -
0.20 -
0.10 ■
n nn -
-LDL = 0.35
-UDLxbar
Gavg
-LDLxbar
-Photochemical
(b)
0.60
0.50
0.40 -
o
?, 0.30
2
0.20
0.10 -
00
UDL = 0.52
aj[i0 2
***n mb
Grand Avg_
0.41
LDL = 0.29
Gavg
(0
0.50
0.45
0.40
0.35
o0.30
J 0.25
Z 0.20
0.15
0.10 ■-
0.05 -
0.00
UDL = 0.47
o
^ip2
Grand Avq_
--
^a MB
0.37
"LDL ■ 0.26
-
-UDLxbar
Gavg
-LDLxbar
■Photochemical
Figure 4-61. Significance of Ti0 2 vs MB on E. coli Destruction, Based on
ANOM, in Combination Experiments; (a) 5 Minutes (b) 15
Minutes (c) 30 Minutes
145
(a)
0.80
070 4uDL = 0.63
60 Ti0;
050 4 \ S
%0.AO
z
0.30 -j LDL = 0.35
0.20
0.10
0.00
Both
-UDLxbar
Gavg
Grand Avg
-LDLxbar
-Photochemical
(b)
60
0.50 -
UDL = 0.52
n,Ti02
0.40 ■
Grand Av<
L
0.40
^0.30 -
z
0.20 ■
Tl Both
LDL = 0.28
0.10 -
00 -
Gavg
— O— - Photochemical
(0
0.60
0.50
0.40
>,0.30
0.20
0.10
0.00
UDL = 0.50
T1O2
Grand Avq
Both
fj4D
LDL = 0.30
-UDLxbar
Gavg
-LDLxbar
-Photochemical
Figure 4-62. Significance of Ti0 2 vs Both onE. coli Destruction, Based on
ANOM, in Combination Experiment; (a) 5 Minutes (b) 15
Minutes (c) 30 Minutes
146
(a)
(b)
(0
060
0.50
0.40 -
1 0.3,
z
0.20
0.10
0.00
UDL = 0.51
MB
□ -
Grand Avq
0.37
-'
Both
LDL = 0.23
-UDLxbar
Gavg
■LDLxbar
■Photochemical
0.60
0.40
o
^0.30
2
0.20
0.10
0.00
- UDL = 0.45
MB
Grand Avg
Both
0"53
LDL = 0.21
-UDLxbar
Gavg
-LDLxbar
-Photochemical
0.60
0.50
0.40
>0.30
z
0.20
0.10
0.00
. UDL = 0.43
MB ""^
^-Q Both
Grand Avg
7T32
LDL = 0.22
■UDLxbar
Gavg
-LDLxbar
■Photochemical
Figure 4-63. Significance of MB vs Both on E. coli Destruction, Based on
ANOM, in Combination Experiments; (a) 5 Minutes (b) 15
Minutes (c) 30 Minutes
147
(a)
- Control
-TI02
MB
Both
50 100
Time (minutes)
000
50 100
Time (minutes)
■ Control
-Ti02
-MB
-Both
(b)
Figure 4-64. Normalized Concentration as a Function of Time in Combination
Experiments I Tot A _ = 433-833 W/m 2 , 1^ Avg = 25-40 W/m 2 ; (a)
, Avg
Benzene (b) Toluene
Table 4-31. Mean Concentration (ppb) of Benzene (±120) and Toluene (±199)
in Combination Experiments; I Tot Avg = 433-833 W/m 2 , 1^ Avg = 25-40 W/m 2
Benzene
Time (min)
30
120
Sunlight Dark
Control
.-.-^-.-.-.-.-.-.-.-.-.-.-.•.-.•.•.■.•.•.■.■.■.•.■.•.•.-:*.'.-.-.*:->.
Sunlight Dark
0.01% TiO,
542
459
430
649
640
535
576
233
17
677
620
588
5 mg/L MB
Both
490 672
549 714
30
485 644
372 607
120
421 538
231 581
Toluene
Sunlight Dark
Sunlight Dark
Time (min)
Control
0.01% Ti0 2
413 445
439 447
30
348 436
148 428
120
320 392
1 387
5 mg/L MB
Both
371 462
451 456
30
352 448
254 437
120
293 315
128 393
148
(a)
1 00
UDL = 0.99
□ MB
0.90
l-Qontrol /
Grand Avg
0.80
Ti0 2
0.84
O
o
~$0.70
O
bBoth
LDL = 0.70
0.60
0.50
n An .
-UDLxbar
Gavg
■LDLxbar
■Photochemical
(b)
■UDLxbar
Gavg
Grand Avg
-- (TS9" - -
Both
■LDLxbar
■Photochemical
Figure 4-65. Significance of Photochemical on Benzene Destruction, Based
on ANOM, in Combination Experiments; (a) 30 Minutes (b) 120
Minutes
149
(a)
1-0 UDL = 0.96
0.90
0.80
O
1*0.70
O
0.60
0.50
0.40
LDL = 0.65
■UDLxbar
Gavg
Grand_Aya
Both
■LDLxbar
■Photochemical
(b)
0.80
0.75
0.70
0.65
o 0.60
O
^0.55
"0.50
0.45
0.40
0.35
0.30
-- UDL = 0.74
q Control MB
--
A f\
Grand Avg
-
V
0~53
□ Both
LDL = 0.51
OTi0 2
-UDLxbar
■Gavg
LDLxbar
-O — Photochemical
Figure 4-66. Significance of Photochemical on Toluene Destruction, Based
on ANOM, in Combination Experiments; (a) 30 Minutes (b) 120
Minutes
150
(a)
1.00
0.95
0.90
0.85
o 0.80
O
-&0.75
O
0.70
0.65
0.60
0.55
0.50
UDL = 0.84
--
Both
Grand Ayg_
0.75
--
Ti0 2
j.LDL = 0.65
-UDLxbar
Gavg
-LDLxbar
■Photochemical
(b)
UDL = 0.61
Both
0.60
/ Grand Avg
0.50
/
0.55
J 0.40 -
LDL = 0.48
u
Ti0 2
~S
O 0.30 -
0.20 ■
0.10 -
n nn
-UDLxbar
Gavg
■LDLxbar
-Photochemical
Figure 4-67. Significance of Ti0 2 vs Both on Benzene Destruction, Based on
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120
Minutes
151
(a)
(b)
1 .uu
0.90
UDL = 0.80
80
0.70
^Both
Grand Avg
0"B9
0.60
TioT 3- '
% 050
0.40
LDL = 0.59
0.30 t
0.20 •
0.10
n nn
-UDLxbar
Gavg
-LDLxbar
-Photochemical
0.70
0.60
00.50
o
0.40
0.30 -
20
UDL = 0.56
/'Both
Grand Av<
L
™~7
fJ.38 - '
LDL = 0.40
-LDLxbar
—Photochemical
Gavg
Figure 4-68. Significance of Ti0 2 vs Both on Toluene Destruction, Based on
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120
Minutes
Examination of the ANOM charts showed that differences between
control and Ti0 2 were not apparent until 120 minutes (Figures 4-65 and 4-
66). By 120 minutes, there was a statistically significant difference between
the reactors which contained Ti0 2 only and both the control reactors and
the reactors containing only MB. The inhibitory effect of MB in the
combination reactor was evident for benzene by 120 minutes (Figure 4-67),
though not for toluene (Figure 4-68).
152
Summary
The use of dye in conjunction with Ti0 2 did not enhance the
photochemical process for either disinfection or detoxification. While it had
no apparent effect in the disinfection reactions, the dye acted as an
inhibitory agent in the detoxification process. The reduction of efficacy with
the addition of MB was possibly due to scavenging of hydroxyl radicals by
the MB. While this has not been reported for MB, scavenging has been
reported for other oxidizing agents, such as hydrogen peroxide (Blake 1994).
Kinetic Considerations
For a quantitative comparison of experimental conditions,
experimental reaction rate constants, k, were calculated using the first
order reaction rate equation shown below. Rate constants are presented
only for those experiments in which destruction of contaminants occurred.
ln(CyC) = kt ( 4-7 )
where:
C = Initial concentration (or colony density)
C = Concentration (or colony density) at time, t
t = time, in minutes
k = calculated rate constant (min 1 )
Detoxification
Experimental first order rate constants are presented for the
destruction of benzene, toluene and xylene isomers by Ti0 2 photocatalysis in
UV light, Ti0 2 photocatalysis in sunlight and the use of Ti0 2 photocatalysis
combined with MB. The calculated rate constants are shown in Table 4-32.
153
The higher rate constants correspond to faster reaction time. For Ti0 2
photocatalysis the fastest reaction rate (k = 0.12 min' 1 ) was observed in
reactors illuminated by UV lamps (29 W/m 2 ) which contained 0.01% Ti0 2
and water adjusted to pH 7.
Table 4-32. Experimental First - Order Rate Constants (min 1 ) for Ti0 2
Photocatalytic Experiments
UV Light (29 W/m' 2 ) @ pH 4
0.01% Ti0 2
0.05% Ti0 2
0.10% Ti0 2
Benzene
0.08
0.03
0.009
Toluene
0.11
0.03
0.009
m&p-Xylene
0.09
0.03
0.01
o-Xylene
0.08
0.03
0.02
UV Light (29 W/m 2 ) @ pH 7
0.01% Ti0 2
0.05% Ti0 2
0.10% Ti0 2
Sunlight du^^s 433-853 W/m
Benzene
0.12
0.02
0.006
Toluene
0.12
0.02
0.007
25-4Tw/m 2 )rpH
m&p-Xylene
0.12
0.02
0.007
was not measured
o-Xylene
0.10
0.02
0.01
0.01% Ti0 2
0.01% Ti0 2 & 5 mg/L MB
0.02
0.007
0.04
0.01
N.A.
N. A.
N.A.
N.A.
The calculated first-order reaction rate constants were consistent
with the previous analysis of the data, wherein 0.01% Ti0 2 was found to be
most effective, though not significantly different from 0.05% Ti0 2 . The rate
constants obtained in these experiments were consistent with those
reported by Madabhushi (1997) for indoor tests at a slightly higher UV
intensity (35 W/m 2 ) and 0.1% Ti0 2 . He reported values ranging from 0.1 -
0.15 for p-Xylene and values of 0.13 - 0.14 for all other components. The
values for his outdoor tests also compared favorably to the value obtained in
this experiment. He reported a consistent value of k=0.03 min' 1 with 1^ av =
31-35 W/m 2 and 0.1% Ti0 2 ,compared to 0.02 min 1 in sunlight (I m avg = 25^0
W/m 2 ) with 0.01% Ti0 2 in this study.
154
Disinfection
While reaction rate constants as a function of time have not been
reported for photochemical disinfection, some of the reported results have
appeared to follow first order kinetics with time (Block et al. 1997). Most of
the data fit well to first-order reaction rate kinetics as shown in Table 4-33.
Several graphical examples are given in Figures 4-69 to 4-72. These results
can be used as a basis for comparison of the processes studied in this
research.
Table 4-33. Correlation Statistics for Least Squares Linear Regression of
Kinetic Data; Confidence Level is 95%
UV Light (29 W/m 2 ) @ pH 4 UV Light (29 W/m 2 ) @ pH 7
r 2 p-value r 2 p-vaiue
0.01% fi02 6.84 0.0077 0.97 0.0007
0.05% Ti02 0.90 0.0025 0.96 0.0002
0.10% Ti02 0.44 0.0257 0.55 0.0188
^^^^^^^^^^^9^^2 ""Sta [jrijgg T(e6T 89TV wSjffitT 'j^g^f"
Omg/LMB 0.79 0.0266 0.95 0.0003
0.1 mg/L MB 0.30 0.0415 0.76 0.0009
lmg/LMB N.A. N.A. 0.14 0.0091
5 mg/L MB 0.49 0.0899 N.A. N.A.
10 mg/L MB N.A. N.A. N.A. N.A.
Omg/LRB 0.99 0.0001 0.99 0.0001
0.1 mg/L RB 0.92 0.001 0.81 0.0010
1 mg/L RB 0.95 0.0003 0.95 0.0003
5 mg/L RB 0.91 0.0012 0.91 0.0012
10 mg/L RB 0.88 0.0022 0.88 0.0022
155
A
3.5
/♦
3
z 25
I 2
S 1.5
1
♦ /
+ Observed
Predicted
0.5 ■
n ^
c
) 50 100
150
Time (minutes)
Figure 4-69. Least Squares Linear Regression of First Order Rate Equation
for Disinfection in UV Light (29 W/m 2 ) with 0.05% Ti0 2 and pH
= 4; r 2 = 0.90, p-value = 0.0025
♦ Observed
Predicted
50 100
Time (minutes)
150
Figure 4-70. Least Squares Linear Regression of First Order Rate Equation
for Disinfection in UV Light (29 W/m 2 ) with 0.10% Ti0 2 and pH
= 7; r 2 = 0.55, p-value = 0.019
156
1 fin
1.40 -
1.20 -
- 1.00 -
z
z 0.80
- 0.60 -
» Observed
Predicted
0.40 -
0.20
n nn <
U.UU ^ |
10 20 30
Time (minutes)
Figure 4-71. Least Squares Linear Regression of First Order Rate Equation
for Disinfection in Sunlight (715-775 W/m 2 ) with no
photochemical and pH = 10; r 2 = 0.99, p-value = 0.0001
6 00
5.00
(
►
_4.00 -
z
^ 3 00
2.00 -
/S ♦
+ Observed
Predicted
1.00 -
n nn <
fc< i i
U.UU % I
20 40 60
Time (minutes)
Figure 4-72. ]
fo
Pi
..east Squares Linear Regression of First Order R
r Disinfection in Sunlight (746-856 W/m 2 ) with 1 1
i = 7; r 2 = 0.95, p-value = 0.0003
ate Equation
ng/L RB and
Table 4-34 is a comparison of the experimental first order rate
constants, k, for all of the disinfection experiment sets. Where no values
were reported, the reactions occurred too quickly to accurately calculate a
rate constant. Examination of the experimental rate constants gave a
hierarchy of processes for disinfection. T
he
largest rate constant,
157
corresponding to the fastest reaction time, 0.45 min' 1 , was in the reactors
containing 5 mg/L MB at pH 10, with 0.1 mg/L MB coming in a close second
at 0.24 min 1 . It is important to note that values could not be calculated for
the other concentrations of MB because the reactions occurred too quickly to
collect enough data for determination of rate constants. The calculated rate
constants for all other conditions were similar in value, ranging from 0.09 -
0.01 min 1 .
Table 4-34. First Order Rate Constants for All Photochemical Disinfection
Experiments
UV Light (29 W/m') 9 pH 4 "UV Light (29 W/m a ) # pH 7
0.01% Ti02 0.05 0.03
0.05% Ti02 0.03 0.03
0.10% Ti02 0.01 0.03
6 mg/L MB 0.09 0.07
0.1 mg/L MB 0.24 0.05
1 mg/L MB N.A. 0.07
5 mg/L MB 0.45 N.A.
10 mg/L MB N.A. N.A.
Sunlight '"(715-77S ^^^^^^^W^^^^^^^^^W^W^^^
6m
mg/L RB
0.05
0.1 mg/L RB
0.09
1 mg/L RB
0.09
5 mg/L RB
0.08
10 mg/L RB
0.08
0.06
0.09
0.08
0.08
General Summary of Results
The only process which was effective for destruction of all of the
contaminants was Ti0 2 photocatalysis. A quantitative comparison of the
experimental sets performed in this study is shown in Table 4-35.
158
Table 4-35. Time to Complete Destruction by Photochemical Treatment.
Photochemical
Light
pH
Benzene
Destruction
Bacteria
Destruction
0.1 mg/L MB
1 mg/L MB
5 mg/L MB
10 mg/L MB
0.1 mg/L MB
1 mg/L MB
5 mg/L MB
10 mg/L MB
0.1 mg/L MB
1 mg/L RB
5 mg/L RB
10 mg/L RB
0.1 mg/L RB
1 mg/L RB
5 mg/L RB
10 mg/L RB
0.01% Ti0 2
0.05% Ti0 2
0.10%TiO 2
0.01% Ti0 2
0.05% Ti0 2
0.10%TiO 2
0.01% Ti0 2
TiO ? &MB
Notes: values in
measured.
Sunlight, 665-891 W/m 2
Sunlight, 665-891 W/m 2
Sunlight, 665-891 W/m 2
Sunlight, 665-891 W/m 2
Sunlight, 542-696 W/m 2
Sunlight, 542-696 W/m 2
Sunlight, 542-696 W/m 2
Sunlight, 542-696 W/m 2
Sunlight, 746-856 W/m 2
Sunlight, 746-856 W/m 2
Sunlight, 746-856 W/m 2
Sunlight, 746-856 W/m 2
Sunlight, 715-775 W/m 2
Sunlight, 715-775 W/m 2
Sunlight, 715-775 W/m 2
Sunlight, 715-775 W/m 2
UV, 29 W/m 2
UV, 29 W/m 2
UV, 29 W/m 2
UV, 29 W/m 2
UV, 29 W/m 2
UV, 29 W/m 2
Sunlight, 433-853 lol , 25-40 OT W/m 2
Sunlight, 433-853,,!, 25-40^ W/m 2
7
(20%, 240 min)
240 min
7
(20%, 240 min)
240 min
7
(35%, 240 min)
240 min
7
(23%, 240 min)
120 min
10
(33%, 240 min)
60 min
10
(29%, 240 min)
5 min
10
(23%, 240 min)
120 min
10
(37%, 240 min)
5 min
7
(23%, 240 min)
120 min
7
(19%, 240 min)
(99.7%, 240 min
7
(27%, 240 min)
120 min
7
(26%, 240 min)
240 min
10
(15%, 240 min)
240 min
10
(35%, 240 min)
120 min
10
(36%, 240 min)
120 min
10
(34%, 240 min)
120 min
4
(99%, 60 min)
60 min
4
(78%, 60 min)
(97%, 60 min)
4
(39%, 60 min)
(88%, 60 min)
10
60 min
240 min
10
(74%, 60 min)
240 min
10
(28%, 60 min)
(91%, 60 min)
n m
(94%, 240 min)
30 min
n m
(56%, 240 min)
15 min
() indicate maximum destruction achieved by time indicated; nm = not
In almost all processes in which destruction was observed the key
factors were: (1) the absence and presence of light, (2) the absence and
presence of photochemical, and (3) the concentration of photochemical. The
one exception was in Rose Bengal disinfection experiments, wherein
neither light nor photochemical had any effect. The significance of these
two parameters was indicative of photochemical action. Minimal pH
effects were observed in disinfection with rose bengal. The lack of effect of
RB concentration on disinfection in these experiments indicates that no
photochemical reaction occurred with RB.
CHAPTER 5
SUMMARY AND CONCLUSIONS
Summary
Laboratory scale studies were conducted to assess the potential for
solar photochemistry to serve as a feasible technology for drinking water
treatment. The objectives defined for the research were to (1) assess the
ability of photochemical processes to effect simultaneous treatment of
chemical and microbiological pollutants and (2) to compare efficacies of
photosensitization, photocatalysis and combined photosensitization and
photocatalysis.
Process Efficacy Comparison for Simultaneous Treatment
The three processes investigated were: 1) heterogeneous Ti0 2
photocatalysis, 2) homogeneous dye photosensitization with methylene blue
and rose bengal, and 3) a combination of the heterogeneous and
homogeneous process with Ti0 2 and methylene blue.
Of the three processes, only one, Ti0 2 photocatalysis, successfully
demonstrated simultaneous detoxification and disinfection of the
components tested. The dye sensitization process with methylene blue
achieved disinfection but did not achieve destruction of the chemical
contaminants tested. When the three processes were compared directly (in
the combination experiments), there were no differences in disinfection
159
160
efficacy. However, the Ti0 2 photocatalytic process was significantly more
effective for detoxification.
Drinking Water Quality
Where photochemical action occurred in the systems studied, the
contaminants either were reduced or demonstrated clear potential for
reduction below standard water quality parameters.
The Ti0 2 photocatalytic process was able to meet or exceed the US
EPA maximum contaminant level for benzene of 5 ppb (Kawamura 1991).
The requirements for toluene (1 ppm) and combined xylenes (10 ppm) were
higher than the starting point of this study. Both MB photosensitization
and Ti0 2 photocatalysis exceeded the requirements for total coliform
reduction of < 5% of initial cfu remaining.
These results indicated that, for this type of contaminant, a
photochemical system could easily be designed to meet the WHO drinking
water quality guidelines, which are less stringent than the US EPA
guidelines.
Conclusions
From these studies it was concluded that the use of solar
photochemical technology has potential for drinking water treatment under
certain conditions. Specific conclusions are as follows:
• Ti0 2 photocatalysis is technically feasible for simultaneous
disinfection and detoxification when the contaminants are well
identified
161
• Dye photosensitization is not an effective treatment for
simultaneous disinfection and detoxification of aromatic
hydrocarbons
• The addition of dye does not enhance the Ti0 2 photocatalytic
reaction for either disinfection or the destruction of BTEX
• Ti0 2 photocatalysis in sunlight and under UV light can meet
WHO drinking water standards for disinfection and BTEX
destruction
• Both Ti0 2 photocatalysis and MB photosensitization exhibit
potential as a small scale disinfectant for rural or peri urban
applications
• Photochemical technology may be more appropriate for treatment
of wastewater or contaminated water, than specifically for
drinking water.
Recommendations for Future Work
The following recommendations are made for future work for
photochemical technology:
• Development of inexpensive technology for the separation or
immobilization of catalyst
• Testing of the technology on a broader range of both
microbiological and chemical contaminants, including viruses
• Determination of relative effectiveness of disinfection techology on
specific microbiological species
162
Exploration of a continuous photochemical supply for
photosensitization
Analysis for destruction of sensitizer in photosensitization
Analysis for intermediate formation in both photocatalysis and
photosensitization.
REFERENCES
Abdullah, M., G. K.-C. Low and R. Matthews. "Effects of Common
Inorganic Anions on Rates of Photocatalytic Oxidation of Organic
Carbon Over Illuminated Titanium Dioxide." Journal of Physical
Chemistry 94 (17 1990): 6820-6825.
Abeel, S. M., A. K. Vickers and D. Decker. "Trends in Purge and Trap."
Journal of Chromatographic Science 32 (August 1994): 328-338.
Acher, A. J. "Sunlight Photooxidation of Organic Pollutants in
Wastewater." Water Science and Technology 17 (4/5 1984): 623-632.
Acher, A. J., E. Fischer and Y. Manor. "Sunlight Disinfection of Domestic
Effluent for Agricultural Use." Water Research 28 (5 1994): 1153-1160.
Acher, A. J., E. Fischer, R. Zellengher and Y. Manor. "Photochemical
Disinfection of Effluents - Pilot Plant Studies." Water Research. 24 ( 7
1990): 837-843.
Acher, A. J. and B. J. Juven. "Destruction of Coliforms in Water and
Sewage Water by Dye-Sensitized Photooxidation." Applied and
Environmental Microbiology 33 (5 1977): 1019-1022.
Acher, A. J. and I. Rosenthal. "Dye-sensitized Photo-oxidation - A New
Approach to the Treatment of Organic Matter in Sewage Effluents."
Water Research 11 (1977): 557-562.
Acra, A., M. Jurdi, H. Mu'allem, Y. Karahagopian and Z. Raffoul. Water
Disinfection by Solar Radiation: Assessment and Application .
Ottawa, Ontario, Canada: International Development Research
Centre, 1990.
Aguado, M. A., M. A. Anderson and C. G. Hill, Jr. "Influence of Light
Intensity and Membrane Properties on the Photocatalytic
Degradation of Formic Acid over Ti02 Ceramic Membranes."
Journal of Molecular Catalysis 89 (1/2 1994): 165-178.
Ahmed, S. and D. F. Ollis. "Solar Photoassisted Catalytic Decomposition of
the Chlorinated Hydrocarbons Trichloroethylene and
Trichloromethane." Solar Energy 32 (5 1984): 597-601.
163
164
Aithal, U. S., T. M. Aminabhavi and S. S. Shukla.
"Photomicroelectrochemical Detoxification of Hazardous Materials."
Journal of Hazardous Materials 33 (1993): 369-400.
Al-Ekabi, H., N. Serpone, E. Pelizzetti, C. Minero, M. A. Fox and R. B.
Draper. "Kinetic Studies in Heterogeneous Photocatalysis. 2. Ti0 2 -
Mediated Degradation of 4-Chlorophenol Alone and in a Three-
Componenet Mixture of 4-Chlorophenol, 2, 4,-Dichlorophenol, and
2,4,5-Trichlorophenol in Air-Equilabrated Aqueous Media."
Langmuir 5 (1 1989): 250-255.
Al-Karaghouli, A. A. and A. N. Minasian. "A Floating- Wick Type Solar
Still (Technical Note)." Renewable Energy 6 (1 1995): 77-79.
Andreatta, D., D. T. Yegian, L. Connelly and R. H. Metcalf. "Recent
Advances in Devices for the Heat Pastuerization of Drinking Water in
the Developing World." In 29th Intersocietv Energy Conversion
Engineering Conference in Monterrey. CA . American Institute of
Aeronautics and Astronautics, 1741-1746, 1994.
ASTM. "Standard Practice for Dealing with Outlying Observations." In
Annual Book of ASTM Standards. Designation: E 178-80 . 102-118.
14.02. Philadelphia, PA: American Society for Testing Materials,
1988.
Bahnemann, D., D. Bockelmann and R. Goslich. "Mechanistic Studies of
Water Detoxification in Illuminated Ti02 Suspensions." Solar Energ y
Materials 21 (1-4 1991): 564-583.
Barbeni, M., M. Morello, E. Pramauro, E. Pelizzetti, M. Vincenti, E.
Borgarello and N. Serpone. "Sunlight Photodegradation of 2,3,5-
trichlorophenoxy-acetic Acid and 2,4,5-trichlorophenol on Ti0 2 .
Identification of Intermediates and Degradation Pathway."
Chemosphere 16 (6 1987): 1165-1179.
Barbeni, M., E. Pramauro, E. Pelizzetti, E. Borgarello and N. Serpone.
"Photodegradation of Pentachlorophenol Catalyzed by Semiconductor
Particles." Chemosphere 14(2 1985): 195-208.
Barry, R. G. and R. J. Chorley. Atmonshere. Weather and Climate , sixth
ed., London: Routledge,, 1992.
Bedford, J., J. F. Klausner, D. Y. Goswami and K. S. Schanze.
"Performance of Nonconcentrating Sloar photocatalytic Oxidation
Reactors Part II: Shallow Pond Configuration." Solar Engineering
(1993): 35-41.
165
Bellar, T. A. and J. J. Lichtenber. "Determining Volatile Organics at
Microgram-per-Liter Levels by Gas Chromatography." Journal of the
American Water Works Association (December 1974): 739-744.
Berry, R. J. and M. R. Mueller. "Photocatalytic Decomposition of Crude Oil
Slicks Using TiO^ on a Floating Substrate." Microchemical Journal
50 (1 1994): 28-32.
Blake, D. M. Bibliography of Work on the Photocatalytic Removal of
Hazardous Compounds from Water and Air . NREL/TP-430-6084.
National Renewable Energy Laboratory, Boulder, CO, 1994. Technical
Report.
Blake, D. M., J. Webb, C. Turchi and K. Magrini. "Kinetic and Mechanistic
Overview of Ti0 2 -photocatalyzed Oxidation Reactions in Aqueous
Solution." Solar Energy Materials 24 (1991): 584-593.
Block, S. S., V. P. Seng and D. Y. Goswami. "Chemically Enhanced
Sunlight for Killing Bacteria." Journal of Solar Energy Engineering
119 (February 1997): 85-91.
Burch, J. D. and K. E. Thomas. "Water Disinfection for Developing
Countries and Potential for Solar Thermal Pasteurization." In
International Solar Energy Society in Korea . 1997.
Burkhard, N. and J. A. Guth. "Photodegradation of Atrazine, Atraton and
Ametryne in Aqueous Solution with Acetone as a Photosensitiser."
Pesticide Science 7 (1976): 65-71.
Canoy, N. J. and A. Knudsen. Waterborne Pathogens of the U. S. Virgin
Islands . Technical Report No. 25. Caribbean Research Institute.
College of the Virgin Islands, 1986. Project Report.
Carey, J. H. and B. G. Oliver. "The Photochemical Treatment of
Wastewater by Ultraviolet Irradiation of Semiconductors." Water
Pollution Research Journal of Canada 15 (2 1980): 157-185. "
Carson, R. Silent Spring . Boston, MA: Houghton Miflin, 1962.
Cheremisinoff, N. P., P. N. Cheremisinoff and R. B. Trattner. Chemical
and Non chemical Disinfection . Ann Arbor, MI: Ann Arbor Science,
1981.
Christmas, J. "The International Drinking Water Supply and Sanitation
Decade and Beyond." In Supplying Water and Saving the
Environment for Six Billion People , eds. U. P. Singh and O. J.
Helwig. 12-30. New York, NY: American Society of Civil Engineers,
1990.
166
Ciochetti, D. and R. H. Metcalf. "Pasteurization of Naturally Contaminated
Water with Solar Energy." Applied and Environmental Microbiolog y
47 (2 1984): 223-228.
Clark, S. W. "Key Issues for Regulating Disinfection By-products." In
Regulating Drinking Water Quality , eds. C. Gilbert, E. and E. J.
Calabrese. 135-144. Boca Raton, FL: Lewis Publishers, 1992.
Crosby, D. G. and A. S. Wong. "Photodecomposition of 2,4,5-
Trichlorophenoxyacetic Acid (2,4, 5-T) in Water." Journal of
A gricultural and Food Chemistry 21 (6 1973): 1052-1054.
Das, S., M. Muneer and K. R. Goppidas. "Photocatalytic Degradation of
Wastewater Pollutants. Titanium-dioxide-mediated Oxidation of
Polynuclear Aromatic Hydrocarbons." Journal of Photochemistry
and Photobiologv A: Chemistry 77 (1 1994): 83-88.
Davis, A. P. and C. P. Huang. "The Photocatalytic Oxidation of Sulfur-
Containing Organic Compounds Using Cadmium Sulfide and the
Effect on CdS Photocorrosion." Water Research 10 (10 1991): 1273-1278.
Downes, A. and T. P. Blunt. "Researches on the Effect of Light upon
Bacteria and Other Organisms." Proceedings of the Royal Society of
London 26 (1877): 488-500.
Droste, R. L. and F. E. McJunkin. "Simple Water Treatment Methods." In
Water Supply and Sanitation In Developing Countries , eds. E. J.
Schiller and R. L. Droste. 101-122. Ann Arbor, MI: Ann Arbor
Science Publishers, 1982.
Eisenberg, T. N., E. J. Middlebrook and V. D. Adams. "Sensitized
Photooxidation for Wastewater Disinfection and Detoxification."
Water Science and Technology 19 (Rio 1987a): 1255-1258.
Eisenberg, T. N., E. J. Middlebrooks and V. D. Adams. "Dye Sensitized
Photo-oxidation of Bromacil in Wastewater." In 40th Industrial
Waste Conference. Purdue University. May 14-15. 1985. in West
Lafavette. Indiana . Butterworths, 693-702, 1986.
Eisenberg, T. N., E. J. Middlebrooks and V. D. Adams. "Sensitized
Photooxidation of Bromacil: Pilot, Bench, and Laboratory Scale
Studies." In 42nd Industrial Waste Conference. Purdue University.
Mav 12-14. 1987. West Lafavette. Indiana . Lewis Publishers, 509-518,
1988.
Eisenberg, T. N., E. J. Middlebrooks, V. D. Adams, A. J. Acher and S.
Saltzman. Use of Solar Energy for Wastewater Disinfection for Crop
Irrigation . 1987b.
167
Ellis, K. V. "Water Disinfection: A Review with Some Consideration of the
Requirements of the Third World." Critical Reviews in
Environmental Control 20 (5/6 1991): 341-407.
Farwati, M. A. "Theoretical Study of Multi-Stage Flash Distillation Using
Solar Energy." Energy 22 (1 1997): 1-5.
Foote, C. S. "Mechanisms of Photosensitized Oxidation." Science 162(3857
1968): 963-970.
Fox, M. A., K. E. Doan and M. T. Dulay. "The Effect of the "Inert" Support
on Relative Photocatalytic Activity in the Oxidateive Decomposition of
Alcohols on Irradiated Titanium Dioxide Composites." Research on
Chemical Intermediates 20 (7 1994): 711-722.
Fujioka, R. S. and O. T. Narikawa. "Effect of Sunlight on Enumeration of
Indicator Bacteria Under Field Conditions." A pplied and
Environmental Microbiology 44 (2 1982): 395-401.
Gameson, A. L. H. and J. R. Saxon. "Field Studies on Effect of Daylight on
Mortality of Coliform Bacteria." Water Research 1 (1967): 279-295.
Gerba, C. P., C. Wallis and J. L. Melnick. "Application of Photodynamic
Oxidation to the Disinfection of Tapwater, Seawater, and Sewage
Contaminated with Poliovirus." Photochemistry and Photobiolog y 26
(5 1977a): 499-504.
Gerba, C. P., C. Wallis and J. L. Melnick. "Disinfection of Wastewater by
Photodynamic Action." Journal of the Water Pollution Control
Federation 49 (4 1977b): 575-583.
Glaze, W. H., J. B. Andelman, R. J. Bull, R. B. Conolly, C. D. Hertz, R. D.
Hood and R. A. Pegram. "Determining Health Risks Associated With
Disinfectants and Disinfection By-products: Research Needs."
Journal of the American Water Works Association 85 (3 1993a): 53-56.
Glaze, W. H., J. F. Kenneke and J. L. Ferry. "Chlorinated Byproducts from
the Ti0 2 -Mediated Photodegradation of Trichloroethylene and
Tetrachloroethylene in Water." Environmental Science & Technology
27 (1 1993b): 177-184.
Goswami, D. Y. "Engineering of Solar Photocatalytic Detoxification and
Disinfection Processes." In Advances in Solar Energy. An Annual
Review of Research and Development , ed. K. W. Boer. 165-209. 10.
Boulder, CO: American Solar Energy Society, 1995.
Goswami, D. Y. and C. K. Jotshi. A Review of UV Radiation Based
Treatment of Wastewater . University of Florida, 1992.
168
Goswami, D. Y., J. Klausner, P. Wyness, A. Martin, G. D. Mathur, K.
Schanze, C. Turchi and E. Marchand. Solar Photocatalytic
Treatment of Groundwater at Tyndall AFB: Field Test Results .
University of Florida, 1993. UFME/SEECL-9302.
Hadden, P. L., R. R. Hill, D. Jeffrey-Smith, J. E. L. McDonald, D. R.
Roberts and A. R. Werninck. "Photooxidation of Organic Pollutants
in Aqueous Systems." Poster Presentation at Advanced Oxidation
Technologies (AOTs) -1, 1994.
Harada, K., T. Hisanaga and K. Tanaka. "Photocatalytic Degradation of
Organophosphorous Insecticides in Aqueous Semiconductor
Suspensions." Water Research 24 (11 1990): 1415-1417.
Hazen, T. C. and G. A. Toranzos. "Tropical Source Water." In Drinking
Water Microbiology , ed. G. A. McFeters. 32-53. New York: Springer-
Verlag, 1990.
Higazy, M. G. "A Floating Sponge Solar Still Design and Performance."
International Journal of Solar Energy 17 (1995): 61-71.
Hobbs^M. F., C. P. Gerba, C. Wallis, J. Melnick and J. S. Lennon.
"Photodynamic Inactivation of Infectious Agents." Journal of the
Environmental Engineering Division (ASCE) 103 (EES 1977): 459-472.
Hofstadler, K., R. Bauer, S. Novalic and G. Heisler. "New Reactor Design
for Photocatalytic Wastewater Treatment with Ti02 Immobilized on
Fused-Silica Glass Fibers: Photomineralization of 4-Chlorophenol."
Environmental Science and Technology 28 (4 1994): 670-674.
Howe, E. D. and B. W. Tliemat. "Fundamentals of Water Desalination." In
Solar Energy Engineering , ed. A. A. M. Sayigh. 431-464. New York:
Academic Press, 1977.
Hsiao, C.-Y., C.-L. Lee and D. F. Ollis. "Heterogeneous Photocatalysis:
Degradation of Dilute Solutions of Dichloromethane (CH 2 C1 2 ),
Chloroform (CHC1 3 ), and Carbon Tetrachloride (CC1 4 ) with
illuminated Ti0 2 Photocatalyst." Journal of Catalysis 82 (1983): 418-
423.
Hsieh, J. S. Solar Energy Engineering . Englewood Cliffs, NJ: Prentice-
Hall, Inc., 1986.
Ireland, J. C, P. Klostermann, E. W. Rice and R. M. Clark. "Inactivation
of Escherichia coli by Titanium Dioxide Photocatalytic Oxidation."
Applied a nd Environmental Microbiology 59 (5 1993): 1668-1670.
169
Joyce, T. M., K. G. McGuigan, M. Elmore-Meegan and R. M. Conroy.
"Inactivation of Fecal Bacteria in Drinking Water by Solar Heating."
Applied and Environmental Microbiology 62 (2 1996): 399-402.
Kawaguchi, H. and M. Furuya. "Photodegradation of Monochlorobenzene
in Titanium Dioxide Aqueous Suspensions." Chemosphere 21 (12
1990): 1435-1440.
Kawamura, S. Integrated Design of Water Treatment Facilities . New York:
John Wiley and Sons, Inc., 1991.
Kondo, M. and W. F. Jardim. "Photodegradation of Chloroform and Urea
Using Ag-Loaded Titanium Dioxide as Catalyst." Water Research 25
(7 1991): 823-827.
Kumar, S. and G. N. Tiwari. "Performance Evaluation of an Active Solar
Distillation System." Energy 221 (9 1996): 805-809.
Larson, R. A., D. D. Ellis, H.-L. Ju and K. A. Marley. "Flavin-Sensitized
Photodecomposition of Anilines and Phenols." Environmental
Toxicology and Chemistry 8 (1989): 1165-1170.
Larson, R. A., K. A. Marley and M. B. Schlauch. "Strategies for
Photochemical Treatment of Wastewaters." In Emerg in g
Technologies for Hazardous Waste Management II . eds. D. W.
Tedder and F. Pohland, G. 66-82. Washington, DC: American
Chemical Society, 1991.
Larson, R. A. and E. J. Weber. Reaction Mechanisms in Environmental
Organic Chemistry . Boca Raton: CRC Press, 1994.
Legrini, O., E. Oliveros and A. M. Braun. "Photochemical Processes for
Water Treatment." Chemical Reviews 93 (1993): 671-698.
Li, X., P. Fitzgerald and L. Bowen. "Sensitized Photo-degradation of
Chlorophenols in a Continuous Flow Reactor System." Water
Science and Technology 26 (1/2 1992): 367-276.
Li, X. Z., M. Zhang and H. Chua. "Disinfection of Municipal Wastewater
Sensitized by Photooxidaion." Water Science and Technology 33 (3
1996): 111-118.
Low, G. K.-C., S. R. McEvoy and R. W. Matthews. "Formation of Nitrate
and Ammonium Ions in Titanium Dioxide Mediated Photocatalytic
Degradation of Organic Compounds Containing Nitrogen Atoms."
Environm ental Science and Technology 25 (3 1991): 460-467.
Lu, M.-C., G.-D. Roam, J.-N. Chen and C. P. Huang. "Factors Affecting the
Photocatalytic Degradation of Dichlorvos Over Titanium Dioxide
170
Supported on Glass." Journal of Photochemistry and Photobiologv A:
Chemistry 76 (1/2 1993): 103-110.
Madabhushi, S. "Development of a Solar Photocatalytic Treatment Facility
for Contaminated Ground Water." Master of Science Thesis,
University of Florida, 1997.
Maillard-Dupuy, C, C. Guillard, H. Courbon and P. Pichat. "Kinetics and
Products of the Ti0 2 Photocatalytic Degradation of Pyridine in
Water." Environmental Science and Technology 28 (12 1994): 2176-
2183.
Malik, M. A. S., G. N. Tiwari, A. Kumar and M. S. Sodha. Solar
Distillation . Oxford: Peramon Press, 1982.
Martin, D. F. and M. J. Perez-Cruet. "Preparation of Sterile Seawater
Through Photodynamic Action. Preliminary Screening Studies."
Florida Scientist, 50 (3 1987): 167-176.
Mason, R. L., R. F. Gunst and J. L. Hess. Statistical Design and Analysis of
Experiments: with applications to engineering and science . Wiley
Series in Probability and Mathematical Statistics, eds. V. Barnett, R.
A. Bradley, J. S. Hunter, D. G. Kendall, R. G. Miller, Jr., A. F. M.
Smith, S. M. Stigler and G. S. Watson. New York: John Wiley &
Sons, 1989.
Matsunaga, T., R. Tomada, T. Nakajima, N. Nakamura and T. Komine.
"Continuous-Sterilization System That Uses Photosemicondutor
Powders." Applied and Environmental Microbiology 54 (6 1988): 1330-
1333.
Matsunaga, T., R. Tomada, T. Nakajima and H. Wake.
"Photoelectrochemical sterilization of microbial cells by
semiconductor powders." Federation of European Microbiological
Societes Microbiology Letters 29 (1985): 211-214.
Matthews, R. W. "Photo-oxidation of organic material in aqueous
suspensions of titanium dioxide." Water Research 20 (5 1986): 569-578.
Matthews, R. W. "Photooxidative Degradation of Coloured Organics in
Water Using Supported Catalysts. Ti0 2 on Sand." Water Research 25
(10 1991): 1169-1176.
Melnick, J. L., C. P. Gerba, C. Wallis and M. F. Hobbs. "Photodynamic
Inactivation of Virus in Sewage." In Virus Aspects of Applying
Municipal Was te to Land in University of Florida. Gainesville. FL .
edited by L. B. Baldwin, Institute of Food and Agricultural Sciences,
University of Florida, 25-36, 1976.
171
Mills, A., R. H. Davies and D. Worsley. "Water Purification by
Semiconductor Photocatalysis." Chemical Society Reviews 22 (6 1993):
417-425.
Mopper, K. and R. G. Zika. "Natural Photosensitizers in Sea Water:
Riboflavin and Its Breakdown Products." In Photochemistry of
Environmental Aquatic Systems , eds. R. G. Zika and W. J. Cooper.
174-190. Washington, DC: American Chemical Society, 1987.
Moser, R. H. "Critical Issues in Regulating Microbes and Disinfection By-
products." In Regulating Drinking Water Quality in Boca Raton. FL .
edited by C. Gilbert, E. and E. J. Calabrese, Lewis Publishers, 145-
151, 1992.
Nguyen, T. and D. F. Ollis. "Complete Heterogeneously Photocatalyzed
Transformation of 1,1- and 1,2-Dibromoethane to C0 2 and HBr."
Journal of Physical Chemistry 88 (16 1984): 3386-3388.
Oberg, V. "Photocatalytic Detoxification of Water Containing Volatile
Organic Compounds." Master of Science Thesis, Kungl Tekniska
Hogskolan (Royal Institute of Technology), 1993.
Oliver, B. G. and J. H. Carey. "Photodegradation of Wastes and Pollutants
in Aquatic Environment." In Homogeneous and Heterogeneous
Photocatalvsis . eds. E. Pelizzetti and N. Serpone. 629-650. 174.
Dordrecht: D. Reidel Publishing Company, 1986.
Oliver, L. G. and J. H. Carey. "Ultraviolet disinfection: an alternative to
chlorination." Journal Water Pollution Control Federation 48(11
1976): 2619-2624.
Ollis, D. F. "Contaminant Degradation in Water." Environmental Science
and Technology 19 (6 1985): 480-474.
Ollis, D. F. "Heterogeneous Photocatalysis for Water Purification: Prospects
and Problems." In Homogeneous and Heterogeneous Photocatalvsis .
eds. E. Pelizzetti and N. Serpone. 651-656. 174. Dordrecht: D. Reidel
Publishing Company, 1986.
Ollis, D. F., E. Pelizzetti and N. Serpone. "Heterogeneous Photocatalysis in
the Environment: Application to Water Purification." In
Photocatalvsis. Fun damentals and Applications , eds. N. Serpone and
E. Pelizzetti. 603-637. New York: John Wiley and Sons, 1989.
Packham, R. F. "Chemical Aspects of Water Quality and Health." Journal
of the Institution of Water and Environmental Management 4 (5
1990): 484-488.
Parker, S. B., ed. McGraw-Hill Dictionary of Scientifica nd Technical
Terms. New York: McGraw-Hill Book Company, 1984.
172
Patel, K. B. "The Antimicrobial Effect of Catalyzed Solar Radiation." Master
of Science Thesis, University of Florida, 1993.
Pelizzetti, E., M. Borgarello, C. Minero, E. Pramauro, E. Borgarello and N.
Serpone. "Photocatalytic Degradation of Polchlorinated Dioxins and
Polychlorinated Biphenyls in Aqueous Suspensions of
Semiconductors Irradiated with Simulated Solar Light."
Chemosphere 17 (3 1988): 499-510.
Pelizzetti, E., V. Maurino, C. Minero, V. Carlin, E. Pramauro, O. Zerbinati
and M. L. Tosato. "Photocatalytic Degradation of Atrizine and Other
s-Triazine Herbicides." Environmental Science and Technology 24(10
1990): 1559-1565.
Pelizzetti, E., C. Minero, V. Maurino, A. Sclafani and H. Hidaka.
"Photocatalytic Degradation of Nonylphenol Ethoxylated
Surfactants." Environmental Science and Technology 23 (11 1989):
1380-1385.
Prasad, G. "The Application of Solar Energy in Water Reuse." Journal of
Chemical Technology and Biotechnology 39 (1987): 29-36.
Premalatha, A. and G. Suseela Rajakumar. "Pentachlorophenol
Degradation by Psuedomonas aerusinosa." World Journal of
Microbiology & Biotechnology 10 (3 1994): 334-337.
Pruden, A. L. and D. F. Ollis. "Degradation of Chloroform by Photoassisted
Heterogeneous Catalysts in Dilute Aqueous Suspensions of Titanium
Dioxide." Environmental Science and Technology 17 (10 1983a): 628-
631.
Pruden, A. L. and D. F. Ollis. "Photoassisted Heterogeneous Catalysis: The
Degradation of Trichloroethylene in Water." Journal of Catalysis 82
(2 1983b): 404-417.
Rajvanshi, A. K. "Analytical and Experimental Investigation of the Effect of
Dyes on Solar Distillation." Doctor of Philosophy, University of
Florida, 1979.
Randall, C. M. and R. Bird. "Insolation Models and Algorithms." In Solar
Resources , ed. R. 1. Hulstrom. 61-141. Cambridge, MA: The MIT
Press, 1989.
Saito, T., T. Iwase, J. Horie and T. Morioka. "Mode of Photocatalytic
Bactericidal Action of Powdered Semiconductor Ti0 2 on Mutans
streptococci" Journal of Photochemistry and Photobiology B: Biology
14 (1992): 369-379.
173
Saltiel, C, A. Martin and D. Y. Goswami. "Performance Analysis of Solar
Water Detoxification Systems by Detailed Simulation." Solar
Engineering 1 (ASME 1992 1992): 21-28.
Sargent, J. W. and R. L. Sanks. "Dye Catalyzed Oxidation of Industrial
Wastes." Journal of the Environmental Engineering Division (ASCE)
102 (EE5 1976): 879-895.
Savino, A. and G. Angeli. "Photodynamic Inactivation of E. coli by
Immobilized or Coated Dyes on Insoluble Supports." Water Research
19 (12 1985): 1465-1469.
Sax, N. I. and R. J. Lewis, Sr. Dangerous Properties of Industrial
Materials . 7th ed., Vol. I-III. New York, NY: Van Nostrand
Reinhold, 1989.
Schiavello, M. "Basic Concepts in Photocatalysis." In Photocatalvsis and
Environment , ed. M. Schiavello. 351-360. 237. Kluwer Academic
Publishers, 1988.
Schlauch, M. B. "Sensitized Photodecomposition of Triazine Herbicides."
Master of Science Thesis, University of Illinois, 1987.
Severin, B. F., M. T. Suidan and R. S. Engelbrecht. "Effects of Temperature
on Ultraviolet Light Disinfection." Environmental Science and
Technology 17 (12 1983): 717-721.
Shah, S. K., E. A. McBean and W. A. Anderson. "Preliminary Studies into
the Disinfection of Potable Water Using Solar Radiation." Canadian
Journal of Civil Engineering 23 (2 1996): 373-380.
Singh, A. K. and G. N. Tiwari. "Long-Term Comparative Study of Solar
Distiller System." Energy 18 (11 1993): 1161-1169.
Sjogren, J. C. and R. A. Sierka. "Inactivation of Phage MS2 by Iron-Aided
Titanium Dioxide Photocatalysis." Applied and Environmental
Microbiology 60 (1 1994): 344-347.
Slade, J. S., N. R. Harris and R. G. Chisholm. "Disinfection of Chlorine
Resistent Enteroviruses in Ground Water by Ultraviolet Irradiation."
Water Science and Technology 18 (10 1986): 115-123.
Sommer, B., A. Marino, Y. Solarte, M. L. Salas, C. Dierolf, C. Valiente, D.
Mora, R. Rechsteiner, P. Setter, W. Wirojanagud, H. Ajarmeh, A.
Al-Hassan and M. Wegelin. "SODIS - an emerging water treatment
process." Journal of Water Supply Research and Technology - Anna
46 (3 1997): 127-137.
Stein, J. "Water for the Wealthy." Environment 19 (4 1977): 6-14.
174
Stevens, A. A., L. A. Moore and R. J. Miltner. "Formation and Control of
Non-Trihalomethane Disinfection By-Products." Journal of the
American Water Works Association 81 (8 1989): 54-60.
Teichner, S. J. and M. Formenti. "Heterogeneous Photocatalysis." In
Photoelectrochemistrv. Photocatalvsis and Photoreactors:
Fundamentals and Developments , ed. M. Schiavello. 457-489. 146.
Dordrecht: D. Reidel Publishing Co., 1985.
Thekaekara, M. P. "Solar Radiation Measurement: Techniques and
Instrumentation." Solar Energy 18 (1976): 309.
Tratnyek, P. G., M. S. Elovitz and P. Colverson. "Photoeffects of Textile Dye
Wastewaters: Sensitization of Singlet Oxygen Formation, Oxidation
of Phenols and Toxicity to Bacteria." Environmental Toxicology and
Chemistry 13 (1994): 27-33.
Tseng, J. and C. P. Huang. "Mechanistic Aspects of the Photocatalytic
Oxidation of Phenol in Aqueous Solutions." In Emerg in g
Technologies for Hazardous Waste Management , eds. D. W. Tedder
and F. Pohland, G. 12-39. Washington, DC: American Chemical
Society, 1990.
Tseng, J. M. and C. P. Huang. "Removal of Chlorophenols From Water by
Photocatalytic Oxidation." Water Science and Technology 23 (1/3
1991): 377-387.
Turchi, C. S., L. Edmundson and D. F. Ollis. A pplication of Heterogeneous
Photocatalv sis for the Destruction of Organic Contaminants from a
Paper Mill Alkali Extraction Process . TAPPI 5th International
Symposium on Wood and Pulping Chemistry, Raleigh, NC 1989,
1989. Conference Paper.
Uchida, H., S. Itoh and H. Yoneyama. "Photocatalytic Decomposition of
Propyzamide Using Ti0 2 Supported on Activated Carbon." Chemistry
Letters (12 1993): 1995-1998.
Vidal, A., J. Herrero, M. Romero, B. Sanchez and M. Sanchez.
"Heterogeneous Photocatalysis: Degradation of Ethylbenzene in Ti0 2
Aqueous Suspension." Journal of Photochemistry and Photobiologv
A: Chemistry 79 (3 1994): 213-219.
von Sonntag, C. The Chemical Basis of Radiation Biology . Philadelphia:
Taylor & Francis, Inc., 1987.
Wei, C, W.-Y. Lin, Z. Zainal, N. E. Williams, K. Zhu, A. P. Kruzic, R.
Smith and K. Rajeshwar. "Bactericidal Activity of Ti0 2 Photocatalyst
in Aqueous Media: Toward a Solar-Assisted Water Disinfection
System." Environmental Science and Technology 28 (5 1994): 934-938.
175
Wheeler, D. J. Understanding Industrial Experimentation . 2nd ed.,
Knoxville, TN: SPC Press, Inc., 1990.
WHO. "WHO Calls for New International Partnership on Water and
Sanitation in Africa." Press Release, 1994.
Wieder, S. An Introduction to Solar Energy for Scientists and Engineers .
2nd ed., Malabar, FL: Krieger Publishing Company, 1992.
Wolfe, R. L. "Ultraviolet Disinfection of Potable Water." Environmental
Science and Technology 24 (6 1990): 768-773.
Wyness, P., J. F. Klausner, D. Y. Goswami and K. S. Schanze.
"Performance of Nonconcentrating Solar Photocatalytic Oxidations
REactors Part I: Flat Plate Configuration." Journal of Solar Energy
Engineering 116 (1 1994): 2-7.
Zhang, P., R. J. Scrudato and G. Germano. "Solar catalytic Inactivation of
Escherichia coli in Aqueous Solutions Using Ti0 2 as a Catalyst."
Chemosphere 28 (3 1994a): 607-611.
Zhang, Y., J. C. Crittenden and D. W. Hand. "The Solar Photocatalytic
Decontamination of Water." Chemistry and Industry (19 Sep 1994
1994b): 714-717.
APPENDIX A
EXPERIMENTAL DATA
Control Reactors, TI02.XLS
UV Light @ pH 7
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
1 2
1
2
1
2
1
2
1
2
min
1858.9
1891.9
1021.5
1065.0
696.2
743.9
305.3
320 1
351.6
356.6
5 min
1843.7
1827.4
1000.3
1136.4
568.1
769.5
226.1
327.0
346.9
367.8
15 min
1958.2
1789.1
1062.0
1113.5
587.6
768.8
239.1
330.0
342.4
343.8
30 min
1773.9
1738.2
1028.7
1095.1
568.7
796.8
233.5
341.4
346.4
333.4
60 min
1845.9
1637.5
1052.7
1059.1
5835
746.2
233.9
322.8
339.9
329.7
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
1
2
1
2
1 2
1
2
1
2
min
1839.7
1891.9
997.6
1057.7
679.9
743.9
297.8
320.1
342.9
346.8
5 min
1824.5
1827.4
976.4
1129.0
551.8
769.5
218.6
327.0
338.2
358.0
15 min
1939.0
1789.1
1038.1
1106.2
571.2
768.8
231.6
330.0
333.7
334.1
30 min
1754.7
1738.2
1004.7
1087.7
552.4
796.8
226.1
341.4
337.7
323.6
60 min
1826.6
1637.5
1028.8
1051.8
567.2
746.2
226.5
322.8
331.2
319.9
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor #
1
2
1
2
1
2
1
2
1
2
min
5.36
5.45
2.91
3.05
1.98
2.14
0.87
0.92
0.1
0.1
5 min
5.39
5.10
2.89
3.15
1.63
2.15
0.65
0.91
0.1
0.1
15 min
5.81
5.36
3.11
3.31
1.71
2.30
0.69
099
0.1
0.1
30 min
5.20
5.37
2.97
3.36
1.64
2.46
0.67
1.05
0.1
0.1
60 min
5.52
5.12
3.11
3.29
1.71
2.33
0.68
1.01
0.1
0.1
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor #
1
2
1 2
1
2
1
2
1
2
min
91 6 ppb
932 ppb
471 ppb 497 ppb
303 ppb
333 ppb
102 ppb
1 1 1 ppb
10
10
5 min
922 ppb
869 ppb
467 ppb
51 6 ppb
240 ppb
254 ppb
334 ppb
361 ppb
61 ppb
110 ppb
10
10
15 min
997 ppb
91 4 ppb
508 ppb
544 ppb
70 ppb
123 ppb
10
10
30 min
885 ppb
91 7 ppb
483 ppb
553 ppb
241 ppb
390 ppb
66 ppb
135 ppb
10
10
60 min
943 ppb
872 ppb
507 ppb
540 ppb
255 ppb
367 ppb
68 ppb
127 ppb
10
10
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor #
1
2
1
2
1
2
1
2
min
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
1.01
0.93
0.99
1.04
0.79
1.00
0.60
0.98
15 min
1.09
0.98
1.08
1.10
0.84
1.09
0.69
1.11
30 min
0.97
0.98
1.03
1.11
0.79
1.17
064
1.21
60 min
1.03
0.93
1.08
1.09
0.84
1.10
0.67
1.14
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg
SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
0.97
0.04
1.01
0.02
090
0.11
0.79
0.19
15 min
30 min
1.03
0.05
1.09
0.01
0.96
0.12
0.90
0.21
0.98
0.01
1 07
0.04
0.98
0.19
0.93
0.28
60 mm
0.98
0.05
1.08
0.01
0.97
0.13
0.91
0.23
176
177
Control Reactors, TI02.XLS
Dark @ pH 7
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
9 10
9
10
9
10
9
10
9
10
min
1967.7
1879.6
1477.1
1439.1
1030.6
980.1
408.6
393.5
368.0
339.8
5 min
1824.1
2019.5
1406.9
1493.8
969 9
1038.2
392.6
409.7
3030
350.7
15 min
1960.0
1980.5
1491.7
1538.1
1050.5
1039.3
419.8
411.3
323.0
340.0
30 min
1952.3
^2002.7
1505.0
1526.6
1041.1
1016.1
416.6
418.7
335.8
344.6
60 min
1894.8
2117.4
1408.9
1585.4
1031.0
1050.3
417.2
431.8
327.4
324.2
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
9
10
9
10
9
10
9
10
9
10
Omin
1938.0
1850.0
1435.4
1397.4
999.8
949.3
394.7
379.6
360.7
332.57
5 min
1794.5
1989.8
1365.2
1452.1
939.1
1007.5
378.7
395.8
295.8
343.44
15 min
1930.4
1950.8
1449 9
1496.4
1019.7
1008.5
406.0
397.4
315.7
332.78
30 min
1922.6
1973.0
1463.2
1484.8
1010.3
985.3
402.7
404.8
328.5
337.39
60 min
1865.1
2087.8
1367.1
1543.7
1000.2
1019.5
403.3
417.9
320.2
317.01
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor #
9
10
9
10
9
10
9
10
9
10
min
5.37
5.56
3.98
4.20
2.77
2.85
1.09
1.14
0.1
0.1
5 min
6.07
5.79
4.62
4.23
3.18
2.93
1.28
1.15
0.1
0.1
15 min
6.11
5.86
4.59
4.50
3.23
303
1.29
1.19
0.1
0.1
30 min
5.85
5.85
4.45
440
3.08
2.92
1.23
1.20
0.1
0.1
60 min
5.83
6.59
4.27
4.87
3.12
3.22
1.26
1.32
0.1
0.1
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor #
9
10
9 10
9
10
9
10
9
10
min
91 8 ppb
952 ppb
665 ppb 705 ppb
446 ppb
461 ppb
143 ppb
151 ppb
10
10
5 min
1043 ppb
994 ppb
1006 ppb
780 ppb
710 ppb
520 ppb
476 ppb
176 ppb
153 ppb
10
10
15 min
1052 ppb
776 ppb
759 ppb
529 ppb
493 ppb
177 ppb
161 ppb
10
10
30 min
1004j>pb
1004 ppb
751 ppb
742 ppb
501 ppb
473 ppb
166 ppb
162 ppb
10
10
60 min
1000 ppb
11 37 ppb
71 8 ppb
826 ppb
510 ppb
527 ppb
172 ppb
183 ppb
10
10
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor #
9
10
9
10
9
10
9
10
min
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
1.14
1.04
1.17
1.01
1.16
1.03
1.24
1.01
15 min
1.15
1.06
1.17
1.08
1.19
1.07
1.24
1.06
30 min
1.09
1.05
1.13
1.05
1.12
1.03
1.17
1.07
60 mm
1.09
1.19
1.08
1.17
1.14
1.14
1.21
1.21
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
1.09
0.05
1.09
0.08
1.10
0.07
1.12
0.11
15 min
1.10
0.04
1.12
0.05
1.13
0.06
1.15
0.09
30 min
1.07
0.02
1.09
0.04
1.07
0.05
1.12
0.05
60 mm
1.14
0.05
1.13
0.05
1.14
0.00
1.21
0.00
178
Control Reactors, TI02.XLS
UV Light @ pH 4
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
77
18
17
18
17
18
17
18
17
18
min
1506.97
1502.08
976.19
982.82
469.28
470.8
193.61
200.3
329.9
334.69
5 min
1590.08
1595.19
996 3
1055.99
461.4
491.82
196.22
207.15
314.97
351.29
15 min
1623.54
1591.84
1037.26
1034.55
503.98
493.19
209.46
213.34
325.83
336.04
30 min
1574.43
1461.74
1054.33
1025.17
506.8
544.7
217.5
234.87
330.41
336.48
60 min
306.95
1546.92
238.43
1126.6
136.81
621.13
81.34
264.22
388.04
357.93
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
17
18
17
18
17
18
17
18
17
18
5 min
1590.08
1595.19
996.3
yo/.oz
1055.99
469.28
461.4
470.8
491.82
193.61
196.22
200.3
207.15
329.9
314.97
334.69
351.29
15 min
1623.54
1591.84
1037.26
1034.55
503.98
493.19
209.46
213.34
325.83
336.04
30 min
1574.43
1461.74
1054.33
1025.17
506.8
544.7
217.5
234.87
330.41
336.48
60 min
306.95
1546.92
238.43
1126.6
136.81
621.13
81.34
264.22
388.04
357.93
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor #
17
18
17
18
17
18
17
18
17
18
Omin
4.57
4.49
2.96
2.94
1.42
1.41
0.59
0.60
0.1
0.1
5 min
5.05
4.54
3.16
3.01
1.46
1.40
0.62
059
0.1
0.1
15 min
4.98
4.74
3.18
3.08
1.55
1.47
0.64
0.63
0.1
0.1
30 min
4.77
4 34
3.19
3.05
1.53
1.62
0.66
0.70
0.1
0.1
60 min
0.79
4.32
0.61
3.15
0.35
1.74
0.21
0.74
0.5
0.1
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor #
17
18
17
18
17
18
17
18
17
18
Omin
772 ppb
757 ppb
480 ppb
476 ppb
202 ppb
199 ppb
51 ppb
53 ppb
10
10
5 min
859 ppb
767 ppb
517 ppb
489 ppb
210 ppb
198 ppb
57 ppb
51 ppb
10
10
15 min
847 ppb
802 ppb
521 ppb
502 ppb
225 ppb
210 ppb
61 ppb
59 ppb
10
10
30 min
808 ppb
731 ppb
522 ppb
496 ppb
222 ppb
238 ppb
64 ppb
71 ppb
10
10
60 mm
18 ppb
727 ppb
11 ppb
51 4 ppb
2 ppb
259 ppb
1 ppb
78 ppb
2
10
Normalized C<
incentration
s
Benzene
Toluene
m&p-)
ylene
o-xylene
Reactor it
17
18
17
18
17
18
17
18
min
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
1.11
1.01
1.08
1.03
1.04
0.99
1.13
0.97
15 min
1.10
1.06
1.08
1.05
1.11
1.06
1.20
1.13
30 min
1.05
0.97
1.09
1.04
1.10
1.19
1.26
1.34
60 min
0.02
0.96
0.02
1.08
0.01
1.30
0.02
1.48
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg
SD
Omin
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
1.06
0.05
1 05
003
1.02
0.02
1.05
0.08
15 mm
1.08
0.02
1.07
0.02
1.08
0.03
1.16
04
30 min
1.01
0.04
1.06
002
1.15
0.05
1.30
0.04
60 min
0.49
0.47
0.55
0.53
0.65
0.65
0.75
0.73
179
Control Reactors, TI02.XLS
Dark @ pH 4
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
25
26
25
26
25
26
25
26
25
26
min
1834.74
2089.47
1512.20
1752.57
981.57
1107.61
390.90
463.79
363.74
359.02
5 min
1935.79
2213.77
1716.51
1888.85
1099.80
1207.84
453.91
506.12
358.09
346.97
15 min
1910.17
1883.61
1694.00
1640.92
1081.81
1090.52
443.65
454.70
357.63
363.31
30 min
1857.45
1758.63
1630.87
1537.70
1071.19
994.99
442.80
414.41
374.89
359.73
60 min
1889.55
1917.40
1673.64
1633.89
1058.40
1027.93
439.43
434.51
371.12
359.43
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
25
26
25
26
25
26
25
26
25
26
min
1778.48
2033.21
1425.86
1666.23
910.12
1036.16
355.13
428.02
355.52
350.80
5 min
1879.53
2157.51
1630.17
1802.51
1028 35
1136.39
418.14
470.35
349.87
338.75
15 min
1853.91
1827.35
1607.66
1554.58
1010.36
1019.07
407.88
418.93
349.41
355.09
30 min
1801.19
1702.37
1544.53
1451.36
999.74
923.54
407.03
378.64
366.67
351.51
60 min
1833 29
1861.14
1587.30
1547.55
986.95 I 956.48
403.66
398.74
362.90
351.21
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor »
25
26
25
26
25
26
25
26
25
26
min
5.00
5.80
4.01
4.75
2.56
2.95
1.00
1.22
0.1
0.1
5 min
5.37
637
4.66
5.32
2.94
3.35
1.20
1.39
0.1
0.1
15 mm
5.31
5.15
460
4 38
2.89
2.87
1.17
1.18
0.1
0.1
30 min
4.91
4.84
4.21
4.13
2.73
2.63
1.11
1.08
0.1
0.1
60 min
5.05
5.30
4.37
4.41
2.72
2.72
1.11
1.14
0.1
0.1
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor*
25
26
25
26
25
26
25
26
25
26
Omin
851jjpb
994 ppb
671 ppb j 805 ppb
408 ppb
479jy>b
125 ppb
165 ppb
10
10
5 mm
917ppb j
1098 ppb
788 ppb
908 ppb
477 ppb
552 ppb
161 ppb
196 ppb
10
10
15 min
905 ppb
877 ppb
778 ppb
737 ppb
468 ppb
464 ppb
156 ppb
158 ppb
10
10
30 min
834 ppb
822 ppb
707 ppb
692 ppb
438 ppb
420 ppb
145 ppb
139 ppb
10
10
60 min
859 ppb | 904 ppb
737 ppb
743 ppb
437 ppb
438 ppb
146 ppb
150 ppb
10
10
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor #
25
26
25
26
25
26
25
26
Omin
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
1.08
1.10
1.18
1.13
1.17
1.15
1.28
1.18
15 min
1.06
0.88
1.16
0.92
1.15
0.97
1.24
0.96
30 min
0.98
0.83
1.05
0.86
1.07
0.88
1.16
0.84
60 min
1.01
0.91
1.10
0.92
1.07
91
1.16
091
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg
SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
1.09
0.01
1.15
0.02
1.16
0.01
1.23
0.05
15 min
0.97
0.09
1.04
0.12
1.06
0.09
1.10
0.14
30 min
60 min
0.90
0.96
0.08
0.05
0.96
1.01
0.10
0.09
0.98
0.99
0.10
0.08
1.00
1.04
0.16
13
180
0.01% Ti02, TI02.XLS
UV Ligh
Area
t@pH7
Raw
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
3
4
3
4
3
4
3
4
3
4
Omin
1733.8
1874.1
975.3
1013.4
497.4
529.0
208.5
211.4
321.8
342.87
5 min
1647.1
1395.2
855.7
751.7
417.2
380.6
159.6
154.9
334.2
334.93
15 min
751.6
688.1
367.8
349.6
179.0
177.6
68.8
69.1
290.1
319.29
30 min
445.7
455.6
214.4
219.3
99.3
105.0
35.8
38.5
276.8
334.1
60 min
80.6
78.5
43.1
43.9
23.7
22.7
10.0
0.0
308.5
295.27
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
3
4
3
4
3
4
3
4
3
4
min
1733.8
1874.1
968.0
1006.1
497.4
529.0
208.5
211.4
312.0
333.095
5 min
1647.1
1395.2
848.4
744.3
417.2
380.6
159.6
154.9
324.4
325.155
15 min
751.6
688.1
360.4
342.3
179.0
177.6
68.8
69.1
280.3
309.515
30 mm
445.7
455.6
207.1
212.0
99.3
105.0
35.8
38.5
267.0
324.325
60 min
80.6
78.5
35.8
36 6
23.7
22.7
100
0.0
298.8
285.495
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor It
3
4
3
4
3
4
3
4
3
4
min
5.56
5.63
310
3.02
1.59
1.59
0.67
0.63
10
0.10
5 min
5.08
4.29
2.62
2 29
1.29
1.17
0.49
0.48
0.30
0.30
15 min
2.68
2.22
1.29
1.11
0.64
0.57
0.25
0.22
0.50
0.50
30 min
1.67
1.40
0.78
0.65
0.37
0.32
0.13
0.12
0.98
1.00
60 min
0.27
0.28
0.12
0.13
0.08
0.08
0.03
0.00
0.98
1.00
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor it
3
4
3
4
3
4
3
4
3
4
Omin
951 ppb_
288 ppb
964 ppb
506 ppb
491 ppb
233 ppb
232 ppb
52 ppb
65 ppb
59 ppb
10.00
10.00
5 mm
241 ppb
139 ppb
120 ppb
59 ppb
11 ppb
10 ppb
3.33
3.33
15 min
86 ppb
69 ppb
35 ppb
29 ppb
12 ppb
10 ppb
1 ppb
1 ppb
2.00
2.00
30 min
25 ppb
20 ppb
9 ppb
6 ppb
1 ppb
Oppb
1 ppb
1 ppb
1.02
1.00
60 mm
1 PPb
1 ppb
1 ppb
1 ppb
1 ppb
1 ppb
1 ppb
Oppb
1.02
1.00
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor #
3
4
3
4
3
4
3
4
min
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
0.30
0.25
0.28
0.24
0.25
0.22
0.17
0.17
15 min
0.09
0.07
0.07
0.06
0.05
0.04
0.02
0.02
30 mm
0.03
0.02
0.02
0.01
0.01
0.00
0.02
0.02
60 min
0.00
0.00
0.00
000
0.00
0.00
0.02
0.00
Statistics
Benzene
Toluene
m&p->
ylene
o-xylene
Ava
SD
Avg
SD
Avg
SD
Avg
SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
0.28
0.03
0.26
002
0.24
0.01
0.17
0.00
15 min
0.08
0.01
0.06
0.01
0.05
0.00
0.02
0.00
30 min
0.02
0.00
0.01
000
0.00
0.00
0.02
0.00
AvdSD
0.0047
60 min
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.01
181
0.01% Ti02. TI02.XLS
Reactor it
min
5 min
15 min
30 min
60 min
Reactor it
min
5 min
15 min
30 min
60 min
Re actor tt
min
5 min
15 min
30 min
60 min
Reactor tt
min
Benzene
11
12
1979.7
21 53.9
1966.9
2080.6
2066.3
2142.3
1920.1
2059.5
1976.1
2104 4
Raw Area
Dark@pH7
Toluene
11
1497 2
1485.4
1505.3
1423.4
1498.0
12
1614.6
1601.8
1624.3
1607.6
1596.0
m& p-xylene
11
1014.5
1014.2
992.9
981.9
1025.6
Benzene
11
12
2009.3
1996.5
2176.0
2102.6
2095.9
2164.3
1949.8
2005.7
2081 6
2126.4
Toluene
Adjusted
12
1099.9
1068.6
1113.1
1068.5
1075.4
11
o-xylene
403.9
403.7
408.5
396.3
412.3
11
1538.9
1527.2
1547.0
1465.1
1539.7
12
1642.8
1630.1
1652.5
1635.9
1624.2
m&p-xylene
11
1045.3
1045.0
1023.7
J0 127
1056.4
Benzene
Referenced
12
1128.8
1097.5
1142.0
1097.3
1104.2
12
431.9
430.5
449.6
430.7
433.2
11
o-xylene
417.8
417.6
422.4
410.1
426.2
Toluene
11
12
11
5.98
578
4.58
6.29
6.23
6.13
4.81
6.00
4.60
5.91
5.92
4.44
5.50
6.26
4.23
12
4.36
4.75
4.58
4.66
4.78
m&p - xylene
11
3.11
3.29
3.04
3.07
Benzene
11
Toluene
Concentrations
2.90
12
3.00
3.20
3.16
3.12
3.25
12
445.5
444.0
463.2
444.3
446.7
Chlorobenzene
JJ
328.8
310.4
329.3
322.6
357.2
12
369.7
335.9
353.9
344.4
332.7
Chlorobenzene
11
336.0
317.6
336.5
329.8
11
o-xylene
1.24
1.31
1.26
1.24
1.17
12
11
5 min
15 min
30 min
60 min
1028 p pb
1083 ppb
1073 ppb
991 ppb
1055 ppb
1015 ppb
1031 ppb
774 ppb
81 5 ppb
941 pp b
1017 ppb
1078 ppb
J777pjb_
749 ppb
710 ppb
12
734 ppb
805 ppb
774 p pb
788 p pb
81 1 ppb
m&p- x ylene
11
508 ppb
540 p pb
495 ppb
501 ppb
46 9 ppb
12
487 ppb
524 ppb
51 8 ppb
51 ppb
Benzene
Normalized C oncentrations
533 ppb
12
1.18
1.29
1.28
1.26
1.32
11
o-xylene
170 ppb
183 ppb
1 72 ppb
170 ppb
156 ppb
Reactor it
11
12
Toluene
11
min
5 min
15 min
30 min
60 min
1.00
1.00
1.00
1.05
1.04
0.99
0.92
1.07
1.05
1.04
1.00
1.03
0.97
1.09
0.92
12
1.00
1.10
1.05
1.07
1.10
11
m &p-xylene
1.00
1.06
0.98
0.99
0.92
min
5 min
15 min
30 min
60 min
Avq
Benzene
SD
1.00
1.06
1.04
1.01 "
1.00
0.00
0.01
0.00
_ap2
0.09
Avq
Toluene
Statistics
12
1.00
1.08
1.06
1.05
1.09
12
158 ppb
179 ppb
177 ppb
173 ppb
1 83 ppb
364.4
12
376.8
342.9
360.9
351.
339.7
Sample
Dilution
11
0.1
0.1
0.1
0.1
0.1
12
0.1
0.1
0.1
0.1
0.1
Dilution
Factor
11
10
10
10
12
10
10
10
11
o-xylene
1.00
1.08
1.01
1.00
0.92
SD
1.00
1.08
y)3
1.02
1.01
0.02
JLQ3
0J35
0.09
m&p-xylene
Avq
SD
1.00
1.07
1J32
1.02
1.01
CK50
0.01
0.04
0.03
0.09
12
1.00
1.13
1.12
1.09
1.15
Avq
o-xylene
SD
1.00
1.10
1.06
1.05
1.04
0.00
0.03
0.05
0.05
0.12
10
10
JO
10
AvdSD
0.0356
182
0.01% Ti02, TI02.XLS
UV Light @ pH 4
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
19
20
19
20
19 20
19 20
19
20
min
1448.44
1583.69
987.85
1077.18
451.56 484.74
191.46
203.69
339.72
348.18
5 min
2145.27
3114.01
1416.17
2073.28
611.66 997.62
277.65
419.74
323.47
341.71
15 min
1733.81
1638.23
1081.52
1062.7
511.57 518.21
202.06
213.02
293.28
322.49
30 min
869.28
754.57
494.9
47881
237.25 217.29
95.79
88 98
325.44
295.32
60 min
120.98
188.52
76.94
114.88
36.51 54.39
14.59
21.29
238.02
290.98
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
19
20
19
20
19
20
19 20
19 20
min
1448.44
1563.39
987.85
1056.29
451.56
472.095
191.46
197.825
339.72
335.535
5 min
2145.27
3093.71
1416.17
2052.39
61 1 .66
984.975
277.65
413.875
323.47
329.065
15 min
1733.81
1617.93
1081.52
1041.81
511.57
505.565
204.645
202.06
207.155
293.28
309.845
30 min
869.28
734.27
494.9
457.92
237.25
95.79
83.115
325.44
282.675
60 min
120.98
16822
76.94
93 99
36.51
41 .745
14.59
15.425
238.02
278.335
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor *
19
20
19
20
19
20
19
20
19
20
min
4.26
4.66
2.91
3.15
1.33
1.41
0.56
0.59
0.1
0.1
5 min
6.63
9.40
4.38
6.24
1.89
2.99
0.86
1.26
0.3
0.3
15 min
591
5.22
3.69
3.36
1.74
1.63
0.69
0.67
05
0.3
30 min
2.67
2.60
1.52
1.62
0.73
0.72
0.29
0.29
0.98
05
60 min
0.51
0.60
0.32 0.34
0.15
015
0.06
0.06
0.98
0.98
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor #
19
20
19
20
19
20
19
20
19
20
min
717ppb
788 ppb
471 ppb
51 5 ppb
185 ppb
199 ppb
46 ppb
51 ppb
10.00
10.00
5 min
382 ppb
549 ppb
246 ppb
358 ppb
96 ppb
162 ppb
33 ppb
57 ppb
3.33
3.33
15 min
203 ppb
297 ppb
122 ppb
184 ppb
52 ppb
80 ppb
14 ppb
22 ppb
200
3.33
30 mm
44 ppb
83 ppb
22 ppb
48 ppb
8 ppb
15 ppb
1 PPb
1 ppb
1.02
2.00
60 min
4 ppb
5 ppb
Oppb
1 ppb
1 ppb
1 PPb
1 ppb
1 ppb
1.02
1.02
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor #
19
20
19
20
19
20
19 20
min
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
0.53
0.70
0.52
0.70
0.52
0.81
0.72
1.12
15 min
0.28
0.38
0.26
0.36
0.28
0.40
0.30
0.43
30 min
0.06
0.11
0.05
0.09
0.04
0.08
0.02
0.02
60 min
0.01
0.01
000
0.00
0.01
0.01
0.02
0.02
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avq
SD
Avq
SD
Avg
SD
min
1.00
000
1.00
0.00
1 00
0.00
1.00
0.00
5 min
0.61
0.08
0.61
0.09
0.67
0.15
0.92
0.20
15 min
0.33
0.05
0.31
0.05
0.34
0.06
0.36
0.06
30 min
0.08
0.02
0.07
0.02
0.06
0.02
0.02
0.00
AvdSD
0.0403
60 min
0.01
0.00
000
0.00
0.01
0.00
0.02
0.00
183
0.01% Ti02, TI02.XLS
Dark @ pH 4
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
27 28
27
28
27 28
27 28
27
28
min
1832.27
1732.28
1617.83
1540.56
1052.36
969.51
99291
424.93
408.18
339.32
365.11
5 min
1720.36
1844.29
1506.01
1635 55
1061.41
409 96
452.17
346.64
361.75
15 min
566.18
1837.19
444.72
1690 27
286.89 1066.18
129.3
452.59
351.5
341.46
30 min
4427.07
1620.28
3920.01
3646.46
1469.56
2548.8 1 926.62
1068.19
398.23
359.88
365.47
60 mm
4205.84
1746.93
1505.29
2501.18 1028.34
1049.85
422.13
359.17
353.38
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
27
28
27
28
27
28
27
28
27
28
min
1888.54
1749.70
1704.17
1566.75
1123.82
1017.22
460.70
420 94
347.55
373.88
5 min
1776.63
1861.71
1592.35
1661.74
1040.97
1085.72
445.73
464.93
354.87
370.52
15 min
622.45
1854.61
531 .06
1716.46
358.35
1090.49
165.07
465.35
359.73
35023
30 min
4483.34
1637.70
4006.35
1495 75
2620.26
950.93
1103.96
410.99
368.11
374.24
60 min
4262.11
1764.35
3732.80
1531.48
2572.64
1052.65
1085.62
434.89
367.40
362.15
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor #
27
28
27
28
27
28
27
28
27
28
min
5.43
4.68
4.90
419
3.23
2.72
1.33
1.13
01
0.1
5 min
5.01
5.02
4.49
4.48
2.93
2.93
1.26
1.25
0.1
0.1
15 min
1.73
5.30
1.48
4.90
1.00
3 11
046
1.33
0.1
0.1
30 min
1218
4.38
10.88
4.00
7.12
2.54
300
1.10
0.3
0.1
60 min
11.60
4.87
1016
4.23
7.00
2.91
2.95
1.20
0.3
0.1
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor M
27
28
27 28
27
28
27 28
27
28
min
929 ppb
792 ppb
833 ppb 703 ppb
530 ppb
476 ppb
437 ppb
475 ppb
1 84 ppb
148 ppb
10
10
5 min
851 ppb
855 ppb
757 ppb
757 ppb
172 ppb
172 ppb
10
10
15 min
258 ppb
904 ppb
21 2 ppb
832 ppb
125 ppb
508 ppb
27 ppb
185 ppb
10
10
30 min
71 7 ppb
737 ppb
639 ppb
668 ppb
41 1 ppb
405 ppb
163 ppb
143 ppb
3.333333
10
60 min
682 ppb
827 ppb
595 ppb
71 ppb
404 ppb
471 ppb
160 ppb
162 ppb
3.333333
10
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor It
27
28
27
28
27
28
27
28
mm
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
0.92
1.08
0.91
1.08
0.90
1.09
0.93
1.16
15 min
0.28
1.14
0.25
1.18
0.24
1.16
0.15
1.25
30 min
0.77
0.93
0.77
0.95
0.78
0.93
0.88
0.97
60 min
0.73
1.04
0.71
1.01
0.76
1 08
0.87
1.09
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg
SD
min
1.00
0.00
1.00
0.00
1 00
0.00
1.00
0.00
5 min
1.00
0.08
0.99
0.08
99
0.09
1.04
0.11
15 min
0.71
0.43
0.72
0.46
070
0.46
0.70
0.55
30 min
0.85
08
0.86
0.86
0.09
0.85
0.92
0.07
0.92
0.04
AvdSD
0.1571
60 min
0.89 0.15
0.15
0.16
0.98
0.11
184
0.05% Ti02. TI02.XLS
UV Light @ pH 7
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
5
6
5
6
5
6
5
6
5
6
min
1703.09
1984.40
966.07
1093.10
499.36
562.34
204.64
222.76
295.62
354.80
5min
2883.61
1925.68
1624.48
1056.15
877.49
557.20
355.76
221 .56
331 .78
358.91
15 min
4303.10
1649.94
2385.48
928.49
1316.55
489.98
526.35
197.31
331.19
348.73
30 min
5196.38
1131.51
3145.22
636.48
1649.49
320.56
644 42
127.38
277.81
329.68
60 min
1957.67
3001.18
1032.92
1679.48
545.74
845.64
331.52
336.54
358.78
320.58
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
5
6
5
6
5
6
5
6
5
6
min
1735.04
2016.35
994.69
1121.72
520.18
583.16
214.16
232.28
30296
362.14
5 min
2915.56
1957.63
1681.89
1653.10
1084.77
898.31
578.02
365.28
231 .08
339.12
366.25
15 min
4335.05
5228.33
1989.62
2414.10
957.11
1337.37
510.80
535.87
206.83
338.53
356.07
30 min
1163.46
3173.84
665.10
1670.31
341.38
653.94
136.90
285.15
337.02
60 min
3033.13
1061.54
1708.10
566.56
866 46
341.04
346.06
366.12
327.92
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor #
5
6
5 6
5
6
5
6
5
6
Omin
5.73
5.57
3.28
3.10
1.72
1.61
0.71
0.64
0.1
0.1
5 min
8.60
5.35
4.87
2.96
2.65
1 58
1.08
0.63
0.3
0.1
15 min
12.81
4.72
7.13
2.69
3.95
1.43
1.58
0.58
0.5
0.1
30 min
18.34
3.45
11.13
1.97
5.86
1.01
2.29
0.41
1
0.1
60 min
5.43
9.25
2.90
5.21
1.55
2.64
0.93
1.06
0.5
0.5
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor It
5
6
5
6
5 6
5
6
5
6
min
982 ppb
953 ppb
539 ppb
505 ppb
255 ppb 236 ppb
72 ppb
60 ppb
10.0
10
5 min
501 ppb
91 3 ppb
276 ppb
481 ppb
141 ppb
230 ppb
46 ppb
59 ppb
3.3
10
15 min
453 ppb
800 ppb
247 ppb
431 ppb
132 ppb
204 ppb
46 ppb
50 ppb
2.0
10
30 min
327pj>b
570 ppb
196 ppb
302 ppb
101 ppb
128 ppb
36 ppb
18 ppb
1.0
10
60 min
186 ppb
324 ppb
94 ppb
178 ppb
45 ppb
85 ppb
23 ppb
27 ppb
2.0
2
Normalized Concentrations
Benzene
Toluene
m&p->
cylene
o-xylene
Reactor it
5
6
5
6
5
6
5
6
min
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
0.51
0.96
0.51
0.95
0.55
0.98
0.64
0.97
15 min
0.46
084
0.46
0.85
0.52
0.87
0.64
0.82
30 min
33
0.60
0.36
0.60
0.39
0.54
0.50
0.30
60 min
0.19
0.34
0.17
0.35
0.18
0.36
0.31
0.45
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg
SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
0.73
0.22
0.73
0.22
0.76
0.21
0.81
0.16
15 min
0.65
0.19
0.66
0.20
0.69
0.17
0.73
0.09
30 min
0.47
0.13
0.48
0.12
0.47
0.07
0.40
0.10
60 min
0.26
0.08
0.26
0.09
0.27
0.09
0.38
0.07
185
0.05% Ti02, TI02.XLS
Dark @ pH 7
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor It
13
14
13
14
13
14
13
14
13
14
min
2063.2
2249.1
1550.4
16486
1106.5
1173.3
443.2
468.7
325.27
381.62
5 min
2180.9
2161 7
1624.5
1583.8
1149.1
1122.7
459.8
453.3
339.40
352.98
15 min
2137.0
2255.0
1586.3
1724.5
1120.4
1223.9
4524
484.4
320.88
355.44
30 min
2159.5
2299.6
1627.6
1735.5
1150.4
1210.6
462.4
482.5
338.81
360.49
60 min
2210.1
2097.3
1621.8
1642 2
1180.0
11179
475 5
447.8
350.25
332.81
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
13
14
13
14
13
14
13
14
73
14
min
2085.3
227\.\
15786
1676.9
1135.3
1202.2
456.8
482.3
332.29
388.64
5 min
2202.9
2183.8
1652.7
1612.1
1178.0
1151.6
473.4
466.9
346.42
360.00
15 min
2159.1
2277.0
1614.5
1752.7
1149.2
1252.8
466.0
498.0
327.90
362.46
30 min
2181.6
2321 .7
1655.9
1763.8
1179.3
1239.5
475.9
496.1
345.83
367.51
60 min
2232.2
21194
1650.0
1670.4
1208.9
1146.8
489.0
461.3
357.27
339.83
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor tt
13
14
13
14
73
14
13
14
13
14
Omin
6.28
5.84
4.75
4.31
3.42
3.09
1.37
1.24
0.1
0.1
5 min
6 36
6.07
4.77
4.48
3.40
3.20
1.37
1.30
0.1
0.1
15 min
6.58
6.28
4.92
4.84
3.50
3.46
1.42
1.37
0.1
0.1
30 min
6.31
6.32
4.79
4.80
3.41
3.37
1.38
1.35
0.1
0.1
60 min
6.25
6.24
4.62
4.92
3.38
3.37
1.37
1.36
0.1
0.1
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor #
13
14
13 14
13
14
13 14
13
14
min
1081 ppb
1003 ppb
805 ppb j 726 ppb
563 ppb
560 ppb
505 ppb
" 524 ppb
193 ppb
169 ppb
10
10
5 min
1096 ppb
1137 ppb
1043 ppb
1082 ppb
809 ppb 756 ppb
192 ppb
179 ppb
10
10
15 min
836 ppb 820 ppb
579 ppb
562 ppb
557 ppb
570 ppb
555 ppb
202 ppb
193 ppb
10
10
30 min
1087 ppb
1 089 ppb
81 2 ppb
814 ppb
835 ppb
194 ppb
189 ppb
10
10
60 min
1076 ppb
1074 ppb
781 ppb
556 ppb
192 ppb
190 ppb
10
10
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor #
13
14
13
14
13
14
13
14
min
1.00
1.00
1.00
1.00
1.00
1 00
1.00
1.00
5 min
1.01
1.04
1.00
1.04
0.99
1.04
0.99
1.06
15 min
1.05
1.08
1.04
1.13
1.03
1.13
1.04
1.14
30 min
1.01
1.09
1.01
1.12
1.00
1.10
1 00
1.12
60 min
1.00
1.07
0.97
1.15
0.99
1.10
0.99
1.12
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg
SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
1.03
0.01
1.02 i 0.02
1.02
0.02
1.03
0.03
15 min
1.07
0.01
1.08
0.05
1.08
0.05
1.09
05
30 mm
1.05
0.04
1.06
0.06
1.05
0.05
1.06
0.06
60 min
1.03
0.04
1.06
09
1.05
0.06
1.06
0.07
186
0.05% Ti02, TI02.XLS
UV Light @ pH 4
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor M
21
22
21
22
21
22
21
22
21
22
min
1643.32
1975.62
1097.35
1 1 26.45
501.67
509.00
208.42
204.75
327.1
370.43
5 min
2535.57
1370.45
1654.29
924.44
793.58
430.06
317 14
175.29
313 07
313 96
15 min
2825.57
99667
1899.02
627 49
903.89
295.7
368.85
121.9
305 08
354.33
30 min
2103 24
718.78
1405.59
453.68
656.52
218.60
274.86
87.78
318 05
339.04
60 min
1369.25
709.19
91 4.00
45878
435.61
219.99
173.16
83 53
293.1
316.54
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
21
22
21
22
21 22
21 22
21
22
min
1663.62
1993.07
1118.24
1150.46
514.32
517.27
214.29
204.75
33975
377.11
5 min
2555.87
1387.90
1675.18
948.45
806.23
438.33
323.01
175.29
325.72
320.64
15 min
2845.87
1014.12
1919.91
651.50
916.54
303.97
37472
121.90
317.73
361.01
30 min
2123.54
736.23
1426.48
477.69
669.17
226.87
280.73
87.78
330.70
345.72
60 mm
1389 55
72664
934 89
482.79
448.26
228.26
179.03
83.53
305.75
323.22
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor #
21
22
21
22
21
22
21 22
21
22
min
490
5.29
3.29
3.05
1.51
1.37
0.63
0.54
0.1
0.1
5 min
7.85
433
5.14
2.96
248
1.37
099
0.55
0.2
0.1
15 min
8.96
2.81
6.04
1.80
2.88
0.84
1.18
0.34
0.3
0.1
30 min
6.42
2.13
4.31
1.38
2.02
066
0.85
0.25
0.3
0.2
60 min
4.54
2.25
306
1.49
1.47
0.71
0.59
0.26
0.3
0.3
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor #
21
22
21 22
21
22
21
22
21 22
min
831 ppb
902 ppb
541 ppb
497 ppb
21 9 ppb
1 93 ppb
59 ppb
43 ppb
10.0
10.0
5 min
683 ppb
728 ppb
438 ppb
480 ppb
196 ppb
192 ppb
97 ppb
62 ppb
43 ppb
5.0
10.0
15 min
522 ppb
453 ppb
346 ppb
271 ppb
156 ppb
53 ppb
5 ppb
3.3
10.0
30 min
369 ppb
165 ppb
242 ppb
97 ppb
104 ppb
32 ppb
33 ppb
1 ppb
3.3
5.0
60 min
256 ppb
117 ppb
166 ppb
72 ppb
70 ppb
24 ppb
17 ppb
1 ppb
3.3
3.3
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor #
21
22
21
22
21
22
21
22
■-
mm
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
0.82
0.81
081
0.97
0.90
1.00
1.06
1.02
15 min
0.63
0.50
64
0.55
0.71
0.50
0.90
0.13
30 min
0.44
0.18
45
0.20
0.47
0.16
0.56
0.02
60 min
0.31
0.13
0.31
0.14
0.32
0.12
0.29
0.02
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avq
SD
Avq
SD
Avg
SD
Avq
SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
081
0.01
0.89
0.08
0.95
005
1.04
0.02
15 min
0.57
0.06
0.59
0.05
0.61
0.10
0.51
0.39
30 min
0.31
0.13
0.32
0.13
0.32
0.16
0.29
0.27
60 min
0.22
0.09
0.23
08
0.22
0.10
0.16
0.13
187
0.05% Ti02, TI02.XLS
Reactor #
min
5 min
15 min
30 min
60 min
Reactor #
min
5 min
15 min
30 min
60 min
Reactor #
min
5 min
15 min
30 min
60 min
Reactor #
min
Benzene
Raw Area
Dark @ pH 4
29
1907.03
1834.87
1772.88
1742.16
1791.27
30
1767.5
1834.88
1570.57
1375.2
1704.33
Toluene
29
1681.47
1668.61
1607.79
1543.12
1637.3
30
1547.71
1611.21
1377.59
1065.97
1519.13
m&p-xylene
29
1131.47
1097.55
1073.81
979.25
1078.69
30
1048.55
1072.41
959.79
657.69
963.71
Benzene
29
1924.45
1852.29
1790.30
1759.58
1808.69
30
1784.92
1852.30
1587.99
1392.62
1721.75
Toluene
Adjusted
29
o-xylene
459.78
456.92
441.09
407.88
444.00
29
1707.66
1694.80
1633.98
1569.31
1663.49
30
1573.90
1637.40
1403.78
1092.16
1545.32
m&p-xylene
29
1155.78
1121.86
1098.12
1003.56
1103.00
Benzene
29
5.11
5.13
5.39
4.44
5.06
30
5.05
5.01
4.47
3.78
4.52
Referenced
30
1072.86
1096.72
984.10
682.00
988.02
30
422.82
443.04
406.81
308.63
402.75
29
o-xylene
472.54
469.68
453.85
420.64
456.76
Toluene
29
4.54
4.69
4.92
3.96
4.65
30
4.45
4.43
3.95
2.97
4.06
m&p-xylene
29
3.07
3.11
3.31
2.53
3.08
Benzene
29
5 min
870 ppb
15 min
873 ppb
30 min
60 min
921 ppb
748 ppb
860 ppb
30
J55J^ppb
853 ppb
754 ppb
629 ppb
763 p pb
Concentrations
30
3.04
2.97
2.77
1.85
2.59
30
435.58
455.80
419.57
321.39
Chlorobenzene
29
367.71
35248
323.20
387.67
348.92
30
344.67
360.59
346.52
35955
372.05
Chlorobenzene
29
376.48
361.25
331 .97
415.51
29
o-xylene
1.26
1.30
1.37
1.06
1.28
Toluene
29
766 p pb
794 ppb
836 ppb
661 ppb
787 ppb
30
751 ppb
747 ppb
660 ppb
481 ppb
679 p pb
m&p-xylene
29
500 ppb
507 ppb
544 ppb
403 p pb
503 ppb
30
494 ppb
482 p pb
446 p pb
280j3pb
Benzene
Reactor #
29
min
1.00
5 min
1.00
15 min
1.06
30 min
0.86
60 min
0.99
30
1.00
0.99
0.88
0.73
0.89
Norm alized Concentrations
41 4 ppb
30
1.23
1.23
1.18
0.87
1.09
o-xylene
29
172 ppb
1 80 p pb
1 92 ppb
137 ppb
1 76 p pb
Toluene
29
1.00
1.04
1.09
0.86
1.03
30
1.00
1.00
0.88
0.64
0.90
m&p-xylene
29
1.00
1.01
1.09
0.81
1.00
Benzene
Statistics
30
1.00
0.98
0.90
0.57
0.84
30
168 ppb
1 68 pp b
396.44
357.69
30
353.44
369.36
355.29
368.32
38082
Sample
Dilution
29
0.1
0.1
0.1
0.1
0.1
30
0.1
0.1
0.1
0.1
0.1
Dilution
Factor
29
10
30
10
1 58 ppb
102 ppb
142 ppb
29
o-xylene
1.00
1.05
1.12
0.80
1.02
min
5 min
15 min
30 min
60 mini
Avg
SD
1.00
1.00
0.97
0.80
0.94
0.00
0.01
0.09
0.06
0.05
Avg
Toluene
30
1.00
1.00
0.94
0.61
0.85
SD
m&p-xylene
1.00
1.02
0.99
0.75
0.97
JLQ0
0.02
0.11
0.11
0.06
Avg
SD
1.00
0.99
0.99
0.69
0.92
0.00
0.02
0.09
0.12
0.08
Avg
o-xylene
SD
1.00
1.02
1.03
0.70
0.94
0.00
0.02
0.09
0.09
0.09
10
10
10
10
10
10
10
10
188
0.10% Ti02, TI02.XLS
UV Light @ pH 7
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
7
8
7
8
7
8
7
8
7
8
min
1997.21
1697.92
1156.8
932.8
593.81
450.32
244 95
185.52
409.6
336.98
5 min
1876.06
1868.57
1104.75
1020.28
544.55
503.71
221 .76
205.76
364.06
342.17
15 min
1708.7
1730.76
950.57
949.24
493.06
488.29
200.84
198.16
368.58
360.45
30 min
1363.74
1529.45
786.85
848.59
396.08
427.53
164.46
170.51
361.07
370.85
60 min
1325.77
1039.57
726.26
568.53
367.49
287.22
149 57
116.08
360.44
291.97
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor It
7
8
7
8
7
8
7 8
7
8
min
2029.16
1727.57
1185.42
974.54
614.63
481.11
254.47
199.41
416.94
344 20
5 min
1908.01
1898.22
1133.37
1062.02
565.37
534.50
231.28
219.65
371.40
349.39
15 min
1740.65
1760.41
979.19
990.98
51 3.88
519.08
210.36
212.05
375 92
367.67
30 min
1395.69
1559.10
815.47
890.33
416.90
458.32
173.98
184.40
368 41
378.07
60 mm
1357.72
1069.22
754.88
610.27
388.31
318.01
159.09
129.97
367.78
299.19
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor #
7
8
7
8
7
8
7
8
7
8
Omin
4.87
5.02
2.84
2.83
1.47
1.40
0.61
0.58
0.1
0.1
5 mm
5.14
5.43
3.05
3 04
1.52
1.53
0.62
63
0.1
0.1
15 min
4.63
4.79
2.60
2.70
1.37
1.41
0.56
0.58
0.1
0.1
30 min
3.79
4.12
2.21
2.35
1.13
1.21
0.47
0.49
0.1
0.1
60 min
3.69
3.57
2.05
2.04
1.06
1.06
0.43
0.43
0.1
0.1
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor It
7
8
7
8
7
8
7
8
7
8
Omin
826 ppb
854 ppb
459 ppb
457 ppb
21 1 ppb
198 ppb
55 ppb
49 ppb
10
10
5 min
875 ppb
928 ppb
497 ppb
495 ppb
220 ppb
221 ppb
57 ppb
58 ppb
10
10
15 min
783 ppb
81 2 ppb
41 6 ppb
433 ppb
192 ppb
200 ppb
46 ppb
49 ppb
10
10
30 min
60 mm
631 ppb
691 ppb
345 ppb
371 ppb
149 ppb
164 ppb
30 ppb
33 ppb
10
10
61 3 ppb
592 ppb
31 6 ppb
31 4 ppb
136 ppb
137 ppb
23 ppb
23 ppb
10
10
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor It
7
8
7
8
7
8
7
8
Omin
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
1.06
1.09
1.08
1.08
1.04
1.12
1.04
1.18
15 min
0.95
0.95
0.91
0.95
091
1.01
0.83
0.99
30 min
0.76
0.81
0.75
0.81
0.71
0.83
054
0.66
60 min
0.74
0.69
0.69
0.69
0.64
0.69
0.41
0.47
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg
SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
1.07
0.01
1.08
0.00
1.08
0.04
1.11
0.07
15 min
0.95
0.00
0.93
0.02
0.96
005
0.91
0.08
30 min
0.79
0.02
0.78
0.03
0.77
006
0.60
0.06
60 min
0.72
0.02
0.69
0.00
0.67
0.03
0.44
0.03
189
0.10% Ti02, TI02.XLS
Reactor tt
min
5 min
15 min
30 min
60 min
Reactor #
min
5 min
15 min
30 min
60 min
Reactor It
min
5 min
15 min
30 min
60 min
Reactor t
min
5 min
15 min
30 min
60 min
Benzene
Raw Area
Dark @ pH 7
Toluene
15
16
15
21 78.82
2140.26
1853.33
1724.7
1921.16
2278.49
1649.31
1893.25
1851.61
2180.36
2257.5
1964.28
1820.29
1695.59
1750.2
16
1479.23
1537.86
1459.82
1511.15
1408.06
m&p-xylene
15
1227.72
1189.07
1329.57
1260.78
1240.53
Benzene
Toluene
Adjus ted
16
1042.29
1109.62
1080.59
1062.63
1052.74
15
o-xylene
486.67
480.82
534.1
500.38
505.92
15
16
2200.88
2162.32
2300.55
15
1853.33
1921.16
1893.25
1752.945
1677.555
2202.42
2279.56
1879.855
1964.28
1820.29
1723.835
1778.445
16
1479.23
1537.86
1459.82
1511.15
1408.06
m&p-xylene
15
1256.605
1217.955
1358.455
1289.665
1269.415
Benzene
Referenced
16
1042.29
1109.62
1080.59
1062.63
1052.74
16
412.78
444.5
427.58
433.86
416.06
Chlorobenzene
15
342.72
341.64
386.69
351.19
360.68
15
o-xylene
500.235
494.385
547.665
513.945
51 9.485
Toluene
15
16
6.29
6.20
15
5.10
5.29
5.01
4.81
Reactor tt
min
5 min
15 min
30 min
60 min
min
5 min
15 min
30 min
60 min
5.84
6.15
5.35
4.77
5.56
4.81
6.20
5.33
4.84
16
4.07
4.23
4.12
4.28
4.12
m&p-xylene
15
3.59
3.49
3.45
3.60
3.45
Benzene
Toluene
Concentrations
16
2.87
3.05
3.05
3.01
3.08
16
412.78
444.5
427.58
433.86
41 6.06
15
o-xylene
1.43
1.42
1.39
1.43
1.41
15
16
15
1 084 ppb
1068 ppb
1003 ppb
1058 ppb
1067 ppb
867 ppb
902 ppb
91 3 ppb
852 ppb
816 ppb
952 ppb
909 ppb
809 ppb
81 6 ppb
820 ppb
16
681 ppb
71 1 ppb
691 ppb
71 9 ppb
691 ppb
m&p-xylene
15
595 ppb
577 ppb
569 ppb
597 ppb
570 ppb
16
463 ppb
498 ppb
497 ppb
489 ppb
Benzene
Normalized Concentrations
502 ppb
16
1.13
1.22
1.21
1.23
1.22
15
o-xylene
16
363.73
363.25
354.07
353.25
341 .67
Chlorobenzene
15
349.74
348.66
393.71
358.21
367.7
16
363.73
363.25
354.07
353.25
341 .67
Sample
Dilution
15
0.1
0.1
0.1
0.1
0.1
16
0.1
0.1
0.1
0.1
0.1
Dilution
203 ppb
201 ppb
196 ppb
204 ppb
200 ppb
Toluene
15
16
15
1.00
1.00
1.00
0.98
1.04
0.96
0.92
1.05
0.95
0.98
0.98
1.10
1.05
0.96
0.96
16
1.00
1.04
1.01
1.06
1.01
m&p-xylene
15
1.00
0.97
0.96
1.00
0.96
Benzene
Statistics
16
1.00
1.07
1.07
1.06
1.08
16
150 ppb
166 ppb
163 ppb
167 ppb
165 ppb
15
o-xylene
1.00
0.99
0.97
1.00
0.98
Avg
SD
1.00
1.01
0.99
1.04
1.02
0.00
0.03
0.06
0.06
0.03
Avg
Toluene
SD
1.00
1.00
0.98
1.01
0.99
0.00
0.04
0.03
0.05
0.03
m&p-xylene
Avg
SD
1.00
1.02
1.01
1.03
1.02 ~
0.00
0.05
0.06
0.03
0.06
16
1.00
1.11
1.09
1.11
1.10
Avg
o-xylene
SD
1.00
1.05
1.03
1.06
1.04
Factor
15
16
10
10
10
10
10
0.00
0.06
0.06
0.05
0.06
10
10
10
10
10
190
0.10% Ti02, TI02.XLS
Reactor It
min
5 min
15 min
30 min
60 min
Reactor #
min
5 min
15 min
30 min
60 min
Reactor #
min
5 min
15 min
30 min
60 min
Reactor #
Benzene
23
24
1651.67
1682.29
1553.54
1727.82
1403.71 1
1575.74
1322.98
1305.94
1063.27
1080.04
Raw Area
UV Light @ pH 4
Toluene
23
1100.09
1066.94
95892
867.52
675.39
24
1141.38
1217.19
1078.89
894.61
719.18
m&p-xylene
23
522.23
501.87
448.75
405.00
317.17
Benzene
23
24
1669.12
1699.74
1570.99
1745.27
1421.16
1593.19
1340.43
1080.72
1323.39
1097.49
Toluene
Adjusted
24
532.67
563.75
511.34
421 .79
345.59
23
o-xylene
212.55
210.36
185.63
168.66
130.64
23
1124.10
1090.95
982.93
891.53
699.40
24
1165.39
1241.20
1 1 02.90
918.62
743.19
23
m&p-xylene
530.50
510.14
457.02
413.27
325.44
Benzene
Referenced
24
540.94
572.02
519.61
430.06
353.86
24
215.54
231 .70
206.81
175.05
141.13
23
o-xylene
212.55
210.36
185.63
168.66
130.64
23
Toluene
24
23
4.97
5.06
3.35
4.27
3.93
5.06
2.97
4.48
2.72
3.72
3.83
2.48
3.01
3.37
1.95
24
3.47
3.60
3.10
2.66
2.28
m&p-xylene
23
1.58
1.39
1.26
1.15
0.91
Benzene
Concentrations
24
1.61
1.66
1.46
1.25
1.09
24
215.54
231 .70
206.81
175.05
141.13
Chlorobenzene
23
329.02
360.94
354.80
353.36
352.88
24
328.92
338.23
349.25
338.56
319.37
Chlorobenzene
23
335.70
367.62
361 .48
360.04
23
o-xylene
0.63
0.57
0.51
0.47
0.36
23
Toluene
24
23
min
5 min
15 min
30 min
845 ppb
60 min
71 8 ppb
657 ppb
61 9 ppb
862 ppb
861 ppb
755 ppb
551 ppb
482 ppb
489 ppb
639 ppb
437 ppb
554 ppb
393 ppb
297 ppb
24
573 ppb
596 pp b
506 ppb
426 ppb
357 ppb
m&p-xylene
23
231 ppb
196 ppb
173 ppb
152 ppb
108 ppb
24
236 ppb
245 ppb
2 09 ppb
170 ppb
Benzene
Normalized Concentrations
141 ppb
24
0.64
0.67
0.58
0.51
0.43
23
o-xylene
59 ppb
48 ppb
37 ppb
29 pp b
10 ppb
Reactor #
23
24
Toluene
23
Omin
5 min
15 min
30 min
60 min
min
5 min
15 min
30 min
60 min
1.00
0.85
0.78
0.73 "
0.58"
24
1.00
1.00
0.88
0.74
0.64
1.00
0.87
0.79
0.71
0.54
Avg
Benzene
SD
1.00
0.92
0.83
0.74
0.61
JI00
0.07
0.05
0.00
0.03
Avg
Toluene
1.00
1.04
0.88
0.74
JX62 _
Statistics
m&p-xylene
24
24
61 PPb
66 ppb
50 ppb
36 ppb
23 ppb
359.56
24
335.60
344.91
355.93
345.24
326.05
Sample
Dilution
23
0.1
0.1
0.1
0.1
0.1
24
0.1
0.1
0.1
0.1
0.1
Dilution
Factor
23
10
10
10
10
10
23
23
o-xylene
24
10
10
JO
10
10
1.00
0.85
0.75
0.66
0.47"
24
1.00
1.04
0.88
0.72
0.60
1.00
0.81
0.63
0.49
0.17
1.00
1.09
0.82
0.60
0.37
SD
m&p-xylene
1.00
0.96
0.84
0.73
0.58
0.00
0.08
0.04
0.02
0.04
Avg
SD
1.00
0.94
0.82
0.69
0.53
0.00
0.09
0.07
0.03
0.06
Avg
o-xylene
SD
1.00
0.95
0.72
0.55
0.27
0.00
0.14
0.09
0.05
0.10
191
0.10% Ti02, TI02.XLS
Dark @ pH 4
Raw Area
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor it
31
32
31
32
31
32
31
32
31
32
min
1827.06
1830.94
1617.42
1602.38
1067.34
1062 94
439.03
432.33
358.85
346.21
5 min
1867.72
1820.84
1665.63
1564.75
1112.21
1070.49
447.98
42653
347.16
344.88
15 min
1824.91
1713.21
1563.89
1543.74
1029.51
1048.92
427.31
427.75
348.18
335.78
30 min
1606.19
1786.41
1413.13
1598.49
873.77
1065.27
383.24
438.77
351.52
401.31
60 min
1711.94
1778.02
1519.03
1574.86
96938
1031.9
41 1 .56
428.24
338.77
360.21
Adjusted
Benzene
Toluene
m&p-xylene
o-xylene
Chlorobenzene
Reactor #
31
32
31
32
31
32
31
32
31
32
min
1848.54
1852.42
1655.51
1640.47
1095.15
1090.75
452.05
445.35
366.08
353.44
5 min
1889.20
1842.32
1703.72
1602.84
1 1 40.02
1098.30
461.00
439.55
354.39
352.11
15 min
1846.39
1734.69
1601.98
1581.83
1057.32
1076.73
440.33
440.77
355.41
343.01
30 min
1627.67
1807.89
1451.22
1636.58
901.58
1093.08
396.26
451.79
358.75
408.54
60 min
1733.42
1799.50
1557.12
1612.95
997.19
1059.71
424.58
441.26
346.00
367.44
Referenced
Sample
Benzene
Toluene
m&p-xylene
o-xylene
Dilution
Reactor #
31
32
31
32
31
32
31
32
31
32
min
5.05
5.24
4.52
4.64
2.99
3.09
1.23
1.26
0.1
0.1
5 min
5.33
5.23
4.81
455
3.22
3.12
1.30
1.25
0.1
0.1
15 min
5.20
5.06
4.51
4.61
2.97
3.14
1.24
1.28
0.1
0.1
30 min
4.54
4.43
4.05
4.01
2.51
2.68
1.10
1.11
0.1
0.1
60 min
501
490
4.50
4.39
2.88
2.88
1.23
1.20
0.1
0.1
Concentrations
Dilution
Benzene
Toluene
m&p-xylene
o-xylene
Factor
Reactor #
31
32
31
32
31
32
31
32
31
32
min
859 ppb
894 ppb
764 ppb
785 ppb
486 ppb
503 ppb
168 ppb
173 ppb
10
10
5 min
91 ppb
892 ppb
81 5 ppb
769 ppb
527 ppb
509 ppb
180 ppb
170 ppb
10
10
15 min
885 ppb
860 ppb
761 ppb
780 ppb
483 ppb
51 3 ppb
169 ppb
177 ppb
10
10
30 min
766 ppb
746 ppb
677 ppb
670 ppb
400 ppb
429 ppb
144 ppb
145 ppb
10
10
60 min
852 ppb
831 ppb
760 ppb
740 ppb
466 ppb
467 ppb
167 ppb
162 ppb
10
10
Normalized Concentrations
Benzene
Toluene
m&p-xylene
o-xylene
Reactor #
31
32
31
32
31
32
31 32
min
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
5 min
1.06
1.00
1.07
0.98
1.08
1.01
1.07
99
15 min
1.03
0.96
1.00
0.99
0.99
1.02
1.00
1.03
30 min
0.89
0.83
089
0.85
0.82
0.85
0.86
0.84
60 min
0.99
0.93
0.99
0.94
0.96
0.93
0.99
0.94
Statistics
Benzene
Toluene
m&p-xylene
o-xylene
Avg
SD
Avg
SD
Avg
SD
Avg
SD
min
1.00
0.00
1.00
0.00
1.00
0.00
1.00
0.00
5 min
1.03
0.03
1.02
0.04
1.05
0.04
1.03
0.04
15 min
1.00
0.03
0.99
0.00
1.01
0.01
1.02
0.01
30 mm
0.86
0.03
0.87
0.02
0.84
0.02
0.85
0.01
60 min
096
0.03
0.97
0.03
0.94
0.02
0.96
0.03
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T Adj Area
436.97
474.49
420.43
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1.71
1.75
1.59
Toluene Ref
435 3 ppb
448.6 ppb
393.3 ppb
Toluene Ref
1.00
1.03
0.90
Avg
cfuA. x 10*3
1 .0 mg/L)
Tol Area
445.16
482.68
428.62
Benzene Ref
2.41
2.36
2.18
Benzene Ref
949.3 ppb
925.1 ppb
846.0 ppb
Benzene Ref
1.00
0.97
0.89
C
%Dest
3(
BAdjArea
613.90
636.88
578.17
Adj Area
254.89
270.39
265.00
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354.69
402.78
333.49
Toluene
1.00
1.14
0.94
8
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Benz Area
621.55
644.53
585.82
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254.89
270.39
265
Benzene
863.16
903.75
800.04
Benzene
1.00
1.05
0.93
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T Adj Area
513.26
445.59
407.86
Toluene Ref
2.06
1.48
1.46
Toluene Ref
549.4 ppb
357.1 ppb
351.0 ppb
>
Toluene Ref
1.00
0.65
0.64
Avg
cfu/L x 10*3
Sunlight (pH='
D.1 mg/L)
Tol Area
521.45
453.78
416.05
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Benzene Ref
2.72
1.99
2.02
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Benzene Ref
1091 .4 ppb
759.5 ppb
771.6 ppb
Concentration!
Benzene Ref
1.00
0.70
0.71
E. coli
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BAdjArea
677.25
601.20
564.77
Chloi
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248.93
301.83
279.82
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Toluene
452.47
365.74
317.38
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Toluene
1.00
0.81
0.70
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Benz Area
684.9
608.85
572.42
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248.93
301.83
279.82
Benzene
975.07
840.72
776.36
Benzene
1.00
0.86
0.80
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T Adj Area
672.66
457.27
397.01
Toluene Ref
2.73
1.82
1.35
Toluene Ref
770 ppb
471.6 ppb
314.1 ppb
Toluene Ref
1.00
0.61
0.41
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cfu/L x 10*3
(control)
Tol Area
680.85
465.46
405.20
Benzene Ref
3.00
2.54
1.82
Benzene Ref
1218 ppb
1009.4 ppb
679.6 ppb
Benzene Ref
1.00
0.83
0.56
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1
BAdjArea
737.97
636.62
536.12
Adj Area
246.02
250.58
295.17
Toluene
656.78
380.71
303.48
Toluene
1.00
0.58
0.46
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Benz Area
745.62
644.27
543.77
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246.02
250.58
295.17
Benzene
1082.34
903.29
725.75
Benzene
1.00
0.83
0.67
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547.79
409.36
359.85
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1.79
1.48
1.34
Toluene Ref
461.5 ppb
357.5 ppb
31 1.9 ppb
Toluene Ref
1.00
077
0.68
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80.0
18.0
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cfuA x 10 3
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180.0
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556.45
418.02
368.51
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2.29
2.02
1.91
Benzene Ref
897 5 ppb
771.1 ppb
722.4 ppb
Benzene Ref
1.00
0.86
080
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0.0%
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98.8%
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99.4%
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BAdj Area
700.68
558.93
513.55
Adj Area
305.33
277.08
268.83
Toluene
496.74
319.31
255.85
Toluene
1.00
0.64
0.52
B
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13.8%
9.1%
0.0%
0.0%
141.4%
100.0%
0.0%
Benz Area
721.46
579.71
534.33
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305.33
277.08
268.83
Benzene
1016.46
766.05
685.88
Benzene
1.00
0.75
0.67
A
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11.0
1.6
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TAdjArea
544.97
406.76
342.68
Toluene Ref
1.82
1.42
1.12
Toluene Ref
470.0 ppb
337.5 ppb
241.0 ppb
Toluene Ref
1.00
0.72
0.51
Avq
805
64.0
42.3
12.5
0.3
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0.0
cfuA x 10 J
805.0
640.0
423.3
125.0
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Tol Area
553.63
415.42
351.34
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Benzene Ref
2.35
1.95
1.55
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Benzene Ref
921.2 ppb
741.6 ppb
557.8 ppb
Concentration:
Benzene Ref
1.00
0.81
0.61
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C
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0.0%
20.5%
47.4%
84.5%
99.6%
100.0%
100.0%
7
BAdjArea
702.68
560.73
472.82
Chloi
Adj Area
299.42
287.20
305.26
Cone
Toluene
493.12
315.98
233.85
Normalized
Toluene
1.00
0.64
0.47
£
B
82
81
38
1
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1.9%
18.9%
9.9%
20.0%
141.4%
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Benz Area
723.46
581.51
493.6
Raw Area
299.42
287.2
305.26
Benzene
1019.99
769.23
613.92
Benzene
1.00
0.75
0.60
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TAdjArea
498.88
428.57
358.22
Toluene Ref
1.58
1.52
1.26
Toluene Ref
390.5 ppb
371 .3 ppb
286.1 ppb
Toluene Ref
1.00
0.95
0.73
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78.7
53.7
54.0
42.0
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536.7
540.0
420.0
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Tol Area
507.54
437.23
366.88
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2.01
2.08
1.82
Benzene Ref
768.9 ppb
799.8 ppb
679.5 ppb
Benzene Ref
1.00
1.04
0.88
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0.0%
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31.4%
46.6%
98.7%
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BAdj Area
636.24
586.78
516.39
Adj Area
316.16
282.07
284.36
Toluene
434.05
343.93
253.76
Toluene
1.00
0.79
0.58
B
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18.2%
25.9%
18.9%
28.6%
141.4%
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Benz Area
657.02
607.56
537.17
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316.16
282.07
284.36
Benzene
902.62
815.25
690.89
Benzene
1.00
0.90
0.77
A
61
37
55
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14.3
13.9
10.2
12.0
1.4
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TAdi Area
515.62
405.61
321.93
Toluene Ref
1.23
0.89
0.75
Toluene Ref
154.2 ppb
93.6 ppb
66.9 ppb
Toluene Ref
1.00
0.61
0.43
Avg
71.0
4.3
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522.81
412.80
329.12
Benzene Ref
1.91
1.44
1.27
Benzene Ref
41 1.9 ppb
289.9 ppb
245.1 ppb
Benzene Ref
1.00
0.70
0.59
C
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802.59
653.14
545.31
Adj Area
420.59
453.64
430.14
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141.79
93.73
57.17
Toluene
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0.66
0.40
B
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16.6%
57.6%
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0.0%
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Benz Area
810.42
660.97
553.14
Raw Area
429.2
462.25
438.75
Benzene
400.18
307.06
239.87
Benzene
1.00
0.77
0.60
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Tol Area
504.44
450.67
349.59
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Benzene Ref
1.80
1.72
1.31
'.entrations
Benzene Ref
383.1 ppb
363.0 ppb
257.1 ppb
1 Concentrator
Benzene Ref
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0.95
0.67
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94.9%
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781.75
727.42
570.38
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434.86
422.82
434.04
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133.76
110.27
66.11
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1.00
0.82
0.49
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50.0%
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141.4%
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Benz Area
789.58
735.25
578.21
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443.47
431.43
442.65
Benzene
387.20
353.34
255.49
Benzene
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0.91
0.66
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TAdj Area
522.72
356.44
379.13
Toluene Ref
1.16
0.97
0.79
Toluene Ref
141.3 ppb
107.0 ppb
74.9 ppb
Toluene Ref
1.00
0.76
0.53
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49.0
44.5
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490.0
445.0
110.0
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Tol Area
529.91
363.63
386.32
Benzene Ref
1.77
1.63
1.27
Benzene Ref
377.0 ppb
340.4 ppb
245.5 ppb
Benzene Ref
1.00
0.90
0.65
C
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77.6%
91.8%
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100.0%
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BAdjArea
802.84
601.72
607.59
Adj Area
452.49
368.32
478.66
Toluene
144.89
72.24
82.16
Toluene
1.00
0.50
0.57
B
45
11
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0.0%
1.1%
0.0%
35.4%
100.0%
0.0%
0.0%
3-May-98
Benz Area
810.67
609.55
615.42
Raw Area
461.1
376.93
487.27
Benzene
400.34
275.02
278.68
Benzene
1.00
0.69
0.70
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APPENDIX B
LIGHT MEASUREMENT
The light available for experiments were measured using an Eppley
TUVR Model Ultraviolet Radiometer for UV light, and Eppley PSP
Pyranometer for total sunlight. Both instruments were factory calibrated
for use outdoors. During outdoor experiments, the measurements were
taken continuously for the duration of the experiments. Charts for these
experiments are shown below.
For the experiments conducted in the chamber, the measurements
were taken at the same distance from the lamps as the reactors were
located. The radiometer gave a stable reading over a period of several
hours. The measurement taken for the UV lamps in the chamber was
adjusted to account for the difference in the spectrum from sunlight and
the UV lamps.
The recorder was jammed for about the last half hour of the
Combination Experiment in experimental set three, so that the values for
that experiment are estimated based on measurements before the recorder
jammed and the maximum and minimum values while it was jammed.
260
261
Solar Insolation for Methylene Blue Experiment
Set#1, pH =7
Qon
800
700
^^^^—^^
600
^^^^^
- E 500
^ 400
^
300
200
Average = 684.95 W/m 2
100 -
-
(
) 30 60 90 120 150 180 210
Time (minutes)
240
Solar Insolation for Methylene Blue Experiment
Set #1, pH 10
900
800
700
600
~ E 500
1 400
-
300
200
100
Average = 671.38 W/m 2
J
c
I I I I I \ 1
• 30 60 90 120 150 180 210
Time (minutes)
240
262
Solar Insolation for Methylene Blue Experiment
Set #2, pH = 7
1000
800
600
w
\y- r V r y^
pVT
%
n hh
400
200
Average = 665.16 W/m
' 1 1 1 —
I
2
1
"Will
H 1 1
30 60
90 120 150
Time (minutes)
180 210 240
Solar Insolation for Methylene Blue Experiment
Set #2, pH =10
Average = 542.36 W/m 2
— i 1 1 1 1 1 1
30 60 90 120 150 180 210 240
Time (minutes)
263
Solar Insolation for Methylene Blue Experiment
Set #3, pH = 7
1 nnn
900
800
-^. '
700
600
.
I 500
400
"
300
200
Average = 891.53 W/m 2
100 ■
n
(
I I I I I I I
) 30 60 90 120 150 180 210 240
Time (minutes)
Solar Insolation for Methylene Blue Experiment
Set #3, pH = 10
1200
1000
800
600
400
200
JHM
A
y
A
v
Average = 696.12 W/m 2
Si
H 1 H
30 60 90 120 150 180 210
Time (minutes)
240
264
Solar Insolation for Rose Bengal Experiment
Set #1 , pH 7
900
800
700
600
" E 500 -
> 400
300 -
~
200
Average = 746.05 W/m 2
100
-
n
c
I I I I — f
I 30 60 90 120 150 180 210
Time (minutes)
240
900
800 4
700
600
"fc 500
§ 400
300
200
100
Solar Insolation for Rose Bengal Experiment
Set#1, pH 10
Average = 715.23 W/m 2
+
30 60 90 120 150
Time (minutes)
180 210 240
265
Solar Insolation for Rose Bengal Experiment
Set #2, pH =7
1 nnn
900
~^M
800
^ J ~-^^ r ^ r
700
*
600
| 500
400
-
300
r |
200
100
Average = 856.32 W/m 2
n
(
I I I I I I I
) 30 60 90 120 150 180 210
Time (minutes)
240
Solar Insolation for Rose Bengal
Set #2, pH =10
60
90 120 150
Time (minutes)
180 210 240
266
500
400
300
200
100
Solar Insolation for Rose Bengal Experiment
Set #3, pH =7
Average = 841.34 W/m 2
30 60 90 120 150 180 210 240
Time (minutes)
Solar Insolation for Rose Bengal Experiment
Set #3, pH = 10
1200
1000
800
600
400
200
i
Average = 749.34 W/m 2
30 60
90 120 150
Time (minutes)
180 210 240
267
Solar Insolation for Combination Experiment
Set #1
300
200
100
Average T oT = 779.68 W/m 2
Averageuv = 38.95 W/m 2
30 60 90
Time (minutes)
10
120
-Total
■-UV
920
900
880
§ 860 -, r
Solar Insolation for Combination Experiment
Set #2
60
50
40
S 840 -
o
Average TO T= 852.58 W/m 2
Averageuv= 39.98 W/m 2
c
<
h 30 5
3
20 N
10
30 60 90
Time (minutes)
120
■Total
■UV
268
600
Solar Insolation for Combination Experiment
Set #3
60
200
100
A/
^ v /V-*-~~V '
Average T0 T= 432.79 W/m 2
Average uv = 24.87 W/m 2
r
30 60 90
Time (minutes)
c
<
30 5
3
20
10
Total
UV
120
BIOGRAPHICAL SKETCH
Adrienne Teresa Cooper was born in Baton Rouge, Louisiana, on
August 21, 1962. She received her undergraduate degree in chemical
engineering from the University of Tennessee in June 1984. Following
graduation she joined E. I. DuPont de Nemours and Company, Inc., as an
engineer in the research and development division of the Chemicals &
Pigments Department. She remained with DuPont until 1992 in various
assignments as a chemical engineer, business analyst, and diversity
education consultant.
From 1990 through 1993 she served on the Alumni Executive Board of
the National Society of Black Engineers. She is also a member of the
American Solar Energy Society, the International Society of African
Scientists and the International Solar Energy Society. She is certified as an
Engineer Intern in the state of Florida.
After leaving DuPont and following a brief stint in West Africa, she
enrolled in the doctoral program at the University of Florida Department of
Environmental Engineering Sciences. During her tenure in Gainesville,
she worked as en environmental engineer for the Alachua County
Department of Environmental Protection and as an instructor in college
prep math at Santa Fe Community College.
269
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
'/?->*£?
Thomas L. Crismarf, Chairman
Professor of Environmental
Engineering Sciences
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
D. Yogi Goswami, Cochairman
Professor of Mechanical
Engineering
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Michael Annable
Associate Professor of
Environmental Engineering
Sciences
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Seymour S. Block
Professor Emeritus of
Chemical Engineering
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
3^4>
Paul A. Chadik
Assistant Professor of
Environmental Engineering
Sciences
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
t£S
Jonathan F. K. Earle
Associate Professor of
Agricultural
and Biological Engineering
This dissertation was submitted to the Graduate Faculty of the
Department of Environmental Engineering Sciences in the College of
Engineering and to the Graduate School and was accepted as partial
fulfillment of the requirements for the degree of Doctor of Philosophy.
August, 1998
Winfred M. Phillips
Dean, College of Engineering
Dean, Graduate School
LD
1780
1991
,C776
UNIVERSITY OF FLORIDA
3 1262 08554 8450
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